CN1531604A - High-strength alloyed aluminum-system plated steel sheet and high-strength automotive part excellent in heat resistance and after-painting corrosion resistance - Google Patents
High-strength alloyed aluminum-system plated steel sheet and high-strength automotive part excellent in heat resistance and after-painting corrosion resistance Download PDFInfo
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- CN1531604A CN1531604A CNA028120361A CN02812036A CN1531604A CN 1531604 A CN1531604 A CN 1531604A CN A028120361 A CNA028120361 A CN A028120361A CN 02812036 A CN02812036 A CN 02812036A CN 1531604 A CN1531604 A CN 1531604A
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/62—Quenching devices
- C21D1/673—Quenching devices for die quenching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
- C23C2/29—Cooling or quenching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
Abstract
The present invention provides a hot press method used for producing a high-strength member for an automobile and, in particular, a part which requires high-strength, such as an undercarriage component of an automobile. More specifically, the present invention provides an aluminum plated steel sheet or an aluminum-zinc plated steel sheet suitable for high temperature forming (hot forming) wherein high strength is obtained after high temperature forming, and a method of producing the same. Also, the present invention provides a hot dip aluminum plated steel sheet which suppresses the alloying reaction of a plated layer during press forming and has beautiful appearance, and an aluminum-system plated steel sheet for hot press having excellent after-painting corrosion resistance. Concretely, the present invention is a high-strength aluminum-system plated steel sheet excellent in heat resistance and after-painting corrosion resistance, characterized by having an Fe-Al-system coating containing, in mass, Mn and Cr of more than 0.1% in total on the surface of the steel containing, in mass, C: 0.05 to 0.7%, Si: 0.05 to 1%, Mn: 0.5 to 3%, P: not more than 0.1%, S: not more than 0.1% and Al: not more than 0.2%, and, in addition, one or more element(s) selected from among Ti: 0.01 to 0.8%, Cr: not more than 3% and Mo: not more than 1%, so as to satisfy the following expression (1): Ti + 0.5xMn + Cr + 0.5xMo > 0.4 ... 1
Description
Technical field
The present invention relates to a kind of alloyed aluminum-system plated steel plate, it is applicable to by the parts that need intensity (for example structure unit of auto parts) of high temperature compacting production and the preparation method of described steel plate, specifically, the steel that the present invention relates to the high-intensity parts of a kind of needs (as the chassis assembly of automobile etc.) and be used to prepare this parts.
Background technology
In order to alleviate vehicle weight (being derived from the global environment problem), the steel plate that requires to be used for automobile has high as far as possible intensity.Yet in general, when improving armor plate strength, elongation and r-value reduce, so formability is impaired.Therefore need a kind of steel plate that has high strength, high-mouldability and fixed in shape simultaneously.
A kind of method that addresses this problem is a kind of by retained austenite being transformed into TRIP (phase transformation induced plasticity) steel that martensite prepares, and the use of TRIP steel recently is more and more.Yet although can use the TRIP steel to be equipped with 1 of formability excellence, 000MPa grade high-strength steel plate is difficult to guarantee the good formability of more high-intensity steel plate, and for example, intensity is not less than 1, the ultrahigh-strength steel plates of 500MPa.And, be difficult to solve the problem of fixed in shape by this technology.
In order to address these problems, a kind of warm-pressing technology is arranged, just it is a kind of technology that arouses attention recently, be the another kind of mode of coordinating high strength and high-mouldability.Japanese unexamined patent publication No. publication number 2000-234153 discloses a kind of technology that forms steel plate and utilize the heat that produces between shaping period to gain in strength in heating.The purpose of this technology is by the component in the suitable control steel, at ferritic this steel plate of temperature range internal heating, and utilizes precipitation strength to gain in strength in this temperature range.
Proposed a kind of high tensile steel plate in Japanese unexamined patent publication No. publication number 2000-87183, wherein the yield strength under mold temperature is reduced to the yield strength under the room temperature, is intended to improve the tolerance range of compression moulding.Yet the intensity that obtains by this technology has certain restriction.
As a kind of technology that overcomes this defective, document (SAE discloses a kind of technology in 2001-01-0078), and it is that steel plate is heated to the temperature range that forms austenite one phase, then during compression moulding with its cooling.
This technology is done the moulding problem that has solved high tensile steel plate like this by steel plate is obtained required material performance being not less than to be shaped under 800 ℃ the high temperature, and it is quenched when cooling off after moulding.Yet,, therefore on surface of steel plate, produce oxide compound and need remove these oxide compounds in the process below because this technology relates in atmosphere and heating.(SAE also discloses a kind of aluminum plating process that suppresses this oxidation between heating period in 2001-01-0078) at above-mentioned document.
In addition, can obtain high strength in the following way: at room temperature form after the steel plate, by part steel plate rapid heating and quick cooling are quenched.In this case, by the local heating steel plate, can only improve needs high-intensity this part intensity.Japanese unexamined patent publication No. publication number 2000-83640 discloses a kind of like this technology and has used the steel plate of carbon content at 0.15-0.5% for this reason.
A kind of thermoforming process and a kind of technology that Aludip is used for thermoforming are disclosed in above-mentioned prior art.Yet in these prior aries, when steel plate was heated to the high temperature that is not less than 800 ℃, Fe diffused to the surface and aluminium coat becomes intermetallic compound at short notice, and this paper back is referred to as " aluminum-system coating ".Because this aluminum-system coating is stone and crisp, its produces crack and peels off with powdery sometimes, so after-painting corrosion resistance is impaired receives publicity.Even do not produce the crack, aspect after-painting corrosion resistance, there be the situation of Aludip than other surface-treated steel plate (for example, hot-dip galvanized steel sheet or hot dipping electricity annealing (galvannealed) steel plate) difference.More particularly, after high-temperature molding, estimate after-painting corrosion resistance, and when cut the cut of cross shaped head cutting (for example with), the corrosion of substrate steel is easy to spread along depth direction from this part, and its extension speed is faster than galvanizing of sacrificing the protection against corrosion type or hot dipping electricity annealed sheet steel.
And, also exist the coating that peels off to be deposited on the mould, and during pressing produce the possibility of scar.This be because, although described electrolytic coating can stand the processing of thermoforming, in fact be difficult to whole part is carried out hot-work, and exist described electrolytic coating to be easy in processing postpones and the part of temperature reduction is peeled off problem.Another problem here is that when temperature reduced, quenching made substrate steel form the rigid structure of mainly being made up of martensite, so stress is tending towards raising gradually.
Summary of the invention
The inventor has carried out completely research in order to address the above problem, and finds and can contain Mn and Cr total amount and prepare the coating steel plate (plated steelsheet) with excellent after-painting corrosion resistance greater than 0.1% Fe-Al-system by applying on the surface of steel plate behind the high-temperature molding.All change into aluminum-system coating through the aluminium-system coating after thermoforming and the local fast heating, and this compound is highly brittle, therefore during processing, is easy to produce the crack.The steel plate that is coated with the aluminium system of the present invention definition is meant that Al and Fe content in the coating are at least 70% coating steel plate.And because this coating has electromotive force than substrate steel plate hight, so the corrosion of substrate steel is from the crack, and after-painting corrosion resistance is tending towards reducing.For fear of the reduction of after-painting corrosion resistance, it is very effective that Mn is joined in the described aluminum-system coating.Although the function of Mn is not clear, but it is said that Mn plays a part to make the electromotive force of the electromotive force of Fe-Al-system coating near base steel sheet by the electromotive force of control alloy layer, and except this function, Mn can also be controlled at the shape of phosphate crystal in the phosphatizing (pre-treatment before spraying paint).
By C, Si, Mn, P, S and Al are appointed as the substrate steel component, and add Ti, Cr and Mo (its adding is effective), so that satisfied following equation 1:
Ti+0.5×Mn+Cr+0.5×Mo＞0.4????...1
Thereby can obtain extremely excellent thermotolerance, especially the thermotolerance after the processing.
Estimation is that these elements have quickened the diffusion between Al and the Fe, even and when having produced the crack like this in coating, being reflected between Fe and the Al carried out around fissured, therefore exposes substrate steel hardly to the open air.
And the inventor also learns by adding N, Nb, V, Ni, Cu, B, Sn and Sb as steel constituent, can obtain more excellent after-painting corrosion resistance.
Meanwhile, it also is useful that the electrolytic coating after the Alloying Treatment contains Si, and adding Zn, Mg etc. can obtain better erosion resistance.In order to suppress the crack in the alloy layer, it is important that the Al content in the alloy layer is not more than 35%.And from the angle of after-painting corrosion resistance, the ideal thickness of Fe-Al-system alloy layer is 3-35 μ m.
And in order to overcome the problems referred to above, the inventor influences the factor of the workability of the steel plate that is coated with the aluminium system after having studied Alloying Treatment in great detail, and obtains following knowledge.That is, because the aluminum-system coating and the substrate steel capital are hard, so the internal stress increase, still,, therefore stress is weakened owing between aluminum-system coating and substrate steel, have soft formation, significantly improve so peel off patience.Described soft formation is by the ferrite phase composite, and estimates that the fact that described soft formation is not less than 1 μ m has prevented that the crack in the alloy layer from spreading to substrate steel.
In addition, in order to overcome the problems referred to above, the inventor influences the factor of the workability of the steel plate that is coated with the aluminium system after having studied Alloying Treatment in great detail, and obtains following knowledge.That is, by making the heating condition optimizing can prevent that electrolytic coating from peeling off.Its reason is not clear, but estimate be at heating condition coating by alloying, the complicated variation takes place in phase structure, and the suitable phase structure of workability occurs guaranteeing.Main points of the present invention are as follows:
(1) a kind of high-intensity alloyed aluminum-system plated steel plate with excellent after-painting corrosion resistance is characterized in that having Fe-Al-system coating on the surface of this steel plate, contains total amount in this coating greater than 0.1% Mn and Cr.
(2) a kind of have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that on the surface of this steel plate, having Fe-Al-system coating, in mass, contain total amount in this coating greater than 0.1% Mn and Cr, in mass, this steel plate contains C:0.05-0.7%, Si:0.05-1%, Mn:0.5-3%, P: be not higher than 0.1%, S: be not higher than 0.1% and Al: be not higher than 0.2%, contain one or more in addition and be selected from following element: Ti:0.01-0.8%, Cr: be not higher than 3% and Mo: be not higher than 1%, so that satisfy following equation 1:
Ti+0.5×Mn+Cr+0.5×Mo＞0.4????...1
(3) as the excellent thermotolerance of (2) have and the high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that this steel also contain (in mass) one or more be selected from following element: N: be not higher than 0.1%, Nb: be not higher than 0.1%, V: be not higher than 0.1%, Ni: be not higher than 1%, Cu: be not higher than 1%, B:0.0003-0.03%, Sn: be not higher than 0.1% and Sb: be not higher than 0.1%.
(4) as (1) the thermotolerance and the high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance with excellence, it is characterized in that this steel contains (in mass): C:0.15-0.55%, Si: be not higher than 0.5%, Mn:0.2-3%, P: be not higher than 0.1%, S: be not higher than 0.04%, Al:0.01-0.1% and N: be not higher than 0.01%, and contain one or more and be selected from following element: B:0.0002-0.0050%, Ti:0.01-0.8%, Cr: be not higher than 2%, Mo: be not higher than 1%, Ni: be not higher than 1%, Cu: be not higher than 0.5% and Sn: be not higher than 0.2%.
(5) as (1)-(4) the arbitrary thermotolerance and the high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that described Fe-Al-system coating also contains the Si of 1-20% with excellence.
(6), it is characterized in that the Al concentration in the described Fe-Al-system coating is not higher than 35 weight % as (1)-(5) arbitrary alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts.
(7) as (1)-(6) the arbitrary thermotolerance and the high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that described Fe-Al-system coating also contains one or both among Zn:1-50% and the Mg:0.1-10% with excellence.
(8) as (1)-(7) the arbitrary thermotolerance with excellence and the high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, the thickness that it is characterized in that described Fe-Al-system coating is 3-35 μ m.
(9) a kind of alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts is characterized in that having: the coating of mainly being made up of Fe-Al on the surface of steel plate; Thickness below this coating is from being not less than 2 μ m to 1/10th the ferrite layer that is not more than steel plate thickness; With the substrate steel of below this ferrite layer, mainly forming by martensite.
(10), it is characterized in that aluminum-system coating on the surface of steel plate and the ferrite layer below the intermetallic compounds layer contain Si as (9) the alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts.
(11) as (9) or the alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts of (10), it is characterized in that the hardness of ferrite phase is not higher than 200.
(12) a kind of high-strength automotive part, its be by will by as (1)-(11) at least a portion compression moulding that arbitrary steel is formed form.
(13), it is characterized in that on its surperficial at least a portion, having the plated film that thickness is 1-200 μ m as (12) high-strength automotive part.
(14) a kind of thermoforming process of high-strength vehicle parts, wherein, when adopting thermoforming process to prepare this trolley part, used steel plate is to be that the main metal of forming makes by electroplating on the steel that contains the C that is not less than 0.05 weight % with Al, these parts are to form by compression moulding after the heating under the heating condition longer than the time of following condition A, B, C and D, and at least a portion of described parts is cooled off being not less than under 10 ℃/second the rate of cooling:
A (800 ℃, 13 minutes), B (900 ℃, 6 minutes), C (1,050 ℃, 1.5 minutes), D (1,200 ℃, 0.3 minute).
The accompanying drawing summary
Fig. 1 shows the figure of the total amount of Mn and Cr in the aluminum-system coating to the influence of after-painting corrosion resistance.
Fig. 2 shows Ni, Cu and the add-on of Sn and the figure of the relation between the exposed erosion resistance.
Fig. 3 shows Ni, Cu and the add-on of Sn and the figure of the relation between the after-painting corrosion resistance.
Fig. 4 shows Cr and the add-on of Mo and the figure of the relation between the exposed erosion resistance.
Fig. 5 shows Cr and the add-on of Mo and the figure of the relation between the after-painting corrosion resistance.
Fig. 6 is the three phase diagram of Fe-Al-Si-system under 950 ℃ the temperature.
Fig. 7 is the photo (back scattered electron image) that shows an example of the structure of the present invention of taking by opticmicroscope.
Fig. 8 is the figure that shows the relation between the workability of outer layer thickness and electrolytic coating.
Fig. 9 is the photo (back scattered electron image) that shows an example of the metal construction of the present invention of taking by opticmicroscope.
Figure 10 is the figure that shows by the shape that steel formability of the present invention is obtained.
Figure 11 is the figure that has shown the relation between heat-up time of the present invention and the Heating temperature.
Implement best mode of the present invention
Embodiment 1
Explained later is used for the chemical constitution of steel plate of the present invention.
C: steel plate of the present invention has after moulding and is not less than 1, the high strength of 000MPa, and it is by cooling and thus its thaumatropy is become the main structure of being made up of martensite to obtain fast after the high temperature compacting.Under this meaning, it is ideal that C content is not less than 0.05%, and in order stably to obtain high strength, and it is 0.1% better that this content is not less than.On the other hand, be not less than 0.7% even C content increases to, its intensity is saturated and also be tending towards producing weld crack, so is limited to 0.7% on it.
Si: because Si content is too low makes fatigue characteristic impaired, so its add-on to be not less than 0.05% be ideal.Yet, on surface of steel plate, form the steady oxide film and hinder the performance of aluminizing at Si during the recrystallization annealing.For this reason, Si on be limited to 1%.
Mn:Mn is the element of known reinforcement steel plate hardenability.Equally, Mn prevents the required element of thermal embrittlement that caused by S (being a kind of unavoidable impurities).For this reason, to be not less than 0.5% be preferred to its add-on.And Mn also strengthens the thermotolerance after aluminizing.Yet, make that the erosion-resisting characteristics after quenching is impaired because the Mn add-on surpasses 3%, so this value is defined as its upper limit.
Ti:Ti has the greatest impact to the thermotolerance of aluminium coat.In surpassing 900 ℃ temperature range, use under the situation of steel plate,, preferably add Ti, and its add-on is not less than 0.01% pair, and to obtain this effect be ideal from stable on heating angle as situation of the present invention.Yet, because Ti and C form TiC, reduced the amount of the C that gives intensity, therefore must increase the amount of C corresponding to the add-on of Ti.And the influence of Ti reaches capacity when about 0.8% amount, so this value is defined as its upper limit.
Cr: similar with Mn and Ti, Cr helps improving the thermotolerance after aluminizing.Yet Mn makes the performance of aluminizing impaired by form stable oxide on the surface of steel plate, and its mode is identical with Si.And Cr is a kind of relatively costly element, therefore is limited to 3% on it when adding it.
Mo: similar with Cr to Mn, Ti, Mo also helps improving the thermotolerance after aluminizing, and its adding is an ideal.Yet because Mo is a kind of relatively costly element, and its effect can be saturated, so be limited to 1% on it.
In the present invention, the preferred stable on heating element that improves after aluminizing that adds, such as Ti, Mn, Cr and Mo, its mode satisfies following formula:
Ti+0.5×Mn+Cr+0.5×Mo＞0.4，
Specifically, Ti and Cr have the effect that during heating prevents plating exfoliation.And Mn can add relatively in large quantities and be highly beneficial to thermotolerance.
The present invention also joins P, S and Al in the steel.Yet because the ductility and the fatigue strength of P and Al infringement steel, and S makes its toughness impaired, and therefore each has determined a upper limit to them.Can in steel, contain among Ni, Nb, V, N, Cu, B, Sn and the Sb one or more when needing once in a while in addition.Ni and Cu are favourable to the erosion resistance of steel, and B improves hardenability.
In many cases, steel plate is after with the aluminium coat alloying, the just use of spraying paint then.In these cases, after-painting corrosion resistance is subjected to the influence of the amount of Mn and Cr in the aluminum-system coating.When the amount of these elements is not less than 0.1%, obtain good after-painting corrosion resistance.As the method that adds Mn and Cr, the steel constituent diffusion process is arranged and they are joined method in the plating bath, and as long as its add-on is not less than 0.1%, any one can obtain this effect these two kinds of methods.Known 1-5 can coexist as in the aluminum-system coating mutually, and this depends on galvanized deposition, steel composition, heating condition etc.Because the influence in the phase of near surface is big especially, therefore when analyzing them, preferably use such as the means of EPMA quantitative analyses etc. and measure them, and calculate its mean value, thereby judge by about 5 parts on the cross section in the zone of distance in the surperficial 5 μ m degree of depth.As described later, hot dip aluminum plating under the situation, add Si usually, at this moment, Si also is contained in the aluminum-system coating.Its amount is about 1-20%, and the amount of the Si in the aluminum-system coating of 1-5 phase can have very big variation.Although the Fe-Al-system coating of 1-5 phase can have different compositions, such as Fe-Al-Si-system aluminum-system coating, Fe
2Al
5, FeAl
3, Fe
3The ferrite of Al, FeAl, dissolving Al, or the like, in these are formed arbitrarily,, just can obtain stable after-painting corrosion resistance as long as the total amount of Mn and Cr is not less than 0.1%.Should analyze which phase as for there being many phase times, because known Mn and Cr help improving after-painting corrosion resistance, and corrosion phenomenon is a kind of macroscopic appearance, therefore the inventor thinks: even there are a plurality of phases, by at random about 5 partial analysiss they, and calculate its mean value, can obtain routine information, and do like this, can judge.And, in order to observe the cross section of heating structure afterwards, the nitral etching of 2-3% of regulation cross section.This is because not etched words, can not observe the interface between the ferrite of base metal and dissolving Al.
Aluminized deposition influences erosion resistance, weldability, workability or the like.If deposition is too little, the after-painting corrosion resistance deficiency, and if too big, weldability and workability are impaired.As for workability, it is owing to crisp aluminum-system coating during the compacting after heating is tending towards peeling off.
Aluminum plating method has no particular limits, and can use hot dip process method, electrochemical plating, vacuum deposition method, at clad with method of another metal or the like.The most widely used industrial method is the hot dip process method at present, and often Al-10%Si is used for plating bath, wherein contains Fe as unavoidable impurities.Except these, reported that adding Cr and Mn improve after-painting corrosion resistance.Add element as other, recommend to have Mg, Ti, Zn, Sb, Sn, Cu, Ni, Co, In, Bi, mishmetal etc., and, can use these elements so as long as electrolytic coating mainly is made up of Al.
Not special aluminized pre-treatment of definition of the present invention and aftertreatment.As electroplating pre-treatment, recommend pre-electroplated Ni, Cu, Cr or Fe etc., and can adopt arbitrarily in these.As the plating aftertreatment, recommendation has chromate treating, resin coating to handle or the like, be intended to mainly prevent to get rusty with smooth, and disappearance when still being heated owing to organic resin, so it is not preferred.As for chromate treating, consider preferably to contain chromic processing film, for example electrolytic chromate or the like at present to chromic control.Can use other aftertreatment in addition of inorganic system chromate treating.Also can use aluminum oxide, silicon-dioxide, MoS in advance
2Deng processing, be intended to smooth.
Embodiment 2
Regulate the reason of steel component in the various details embodiment 2.
N is a kind of element that unavoidably comprises and will adds especially when not adding B, still, measures when excessive the essential add-on that increases Ti when adding B and its.As a result, the problem of existence is that the final TiN amount that produces increases and the generation fire crack, and cost also increases.Therefore, be limited to 0.1% on it.
To add B and be in order to improve during the compression moulding or hardenability when cooling off afterwards, and in order to obtain this effect, its adding must be not less than 0.0002%.Yet, when its add-on is excessive, exist the problem of fire crack and this effect saturated.Therefore, be limited to 0.03% on it.
Ni, Cu and Sn have during the compression moulding after heat by changing the effect that the state of alloying aluminium coat during the heat changes the surface crack state, and because they cause the after-painting corrosion resistance of moulding product to improve therefore is important.As for these elements, by the result shown in the Fig. 2 and 3 that obtains by the add-on of measuring Ni, Cu and Sn, exposed erosion resistance and after-painting corrosion resistance with sample after the high-temperature molding in the laboratory test, the inventor finds, in order to obtain above-mentioned effect, have to add Ni, Cu and Sn, so that they can satisfy equation 3.Here, method for measuring under the condition shown in the employing in an embodiment uses the sample of taking from the part of processing after high-temperature molding to estimate its exposed erosion resistance and after-painting corrosion resistance.
(Ni+0.5×Cu+3×Sn)≥0.012????...3
As among Ni, Cu and the Sn each, add excessive N i and make that these effects are saturated and cost is increased that Cu and Sn have the problem that produces surface crack, so the upper limit of each element fixes on 1.0%, 1% and 0.2% respectively.
The not special regulation of the preparation condition of steel plate of the present invention, but preferred preparation condition will be explained below.
The steel casting that will have above-mentioned component, and with the gained flat plate heat directly or after heating, perhaps will cool off the also flat board of reheat, hot rolling.Here, almost can not discern after direct rolling flat plate heat and the reheat rolling between the difference of performance of steel.And the reheat temperature is not specific, still considers productivity preferably it to be adjusted in 1, and 000-1 is in 300 ℃ the scope.
As for hot rolling, can adopt conventional hot rolling method or flat board is connected with each other and rolling continuously hot rolling method when finish rolling.Consider the tolerance range of productivity and steel plate thickness, the polish temperature when preferably controlling hot rolling is not less than the Ar3 invert point.
Adopt ordinary method to carry out hot rolling cooling afterwards.In this case, from the angle of productivity, preferably this cooling temperature is controlled at and is not less than 550 ℃.On the other hand, if cooling temperature is too high, the acid pickling ability is impaired, therefore preferably this cooling temperature is controlled at not to be higher than 750 ℃.
With regard to acid pickling processing or cold-rolling treatment, can use ordinary method, and with regard to ensuing aluminize processing or ensuing aluminizing-zinc processing, also can use ordinary method.That is, under the situation about handling of aluminizing, Si concentration is that 5-12% is suitable in the plating bath, and aluminizing-during zinc handled, Zn concentration was that 40-50% is suitable in the plating bath.
Here,, can use continuous electroplating equipment with non-oxidising furnace or the continuous electroplating equipment that does not have non-oxidising furnace to electroplate, as long as keep normal condition as for the atmosphere in the electroplating processes.Therefore, when producing product of the present invention, do not need special control, and therefore productivity is not interfered.
Under the superincumbent working condition, before plating, surface of steel plate is not carried out metal and electroplate in advance,, also can not produce specific problem even still use when Ni electroplates in advance, Fe electroplates in advance or other metal is pre-electroplates with raising plating performance.
And, even be included in aluminium coat or Mg when being included in aluminium-zinc electrolytic coating as Mg and Zn, can not produce specific problem and can make steel plate with similar performance.
Embodiment 3
At first explain the reason of in embodiment 3, regulating the steel component below according to the present invention.
The adding of C element makes the structure after the cooling be made of martensite, and guarantees quality of materials, and requires its add-on to be not less than 0.15% to be not less than 1,200MPa with proof strength.On the other hand, if add-on is excessive, almost can not guarantees the intensity of shock resistance distortion, so be limited to 0.55% on it.
Si is a kind of solute strengthening element, and cost that can be low relatively increases the intensity of steel plate.Yet,, electroplate performance so with impaired, so be limited to 0.5% on it if its adding is excessive.
It is in order to guarantee intensity after the cooling under the rate of cooling scope widely that Mn adds.
When the big but add-on of Mn of C amount hour, in the scope (this scope can obtain) of conventional rate of cooling, can not obtain martensitic structure during compression moulding, so its intensity can not be guaranteed almost.At steel plate thickness is under the situation of 1.4mm, and the scope of the rate of cooling that this paper quotes as proof is not higher than 500 ℃/second.In order to show this function, require its add-on to be not less than 0.2%.On the other hand, if the Mn amount is too big, not only cost increases, and this effect is saturated.Therefore, be limited to 3% on it.
S a kind ofly comprises inevitably and causes the element that workability is impaired.Therefore, need reduce its amount as much as possible.Be not higher than 0.04% by its amount is reduced to, eliminated the problem of workability, and determine that therefore its content is not higher than 0.04%.
P is a kind of solute strengthening element, and cost that can be low relatively increases the intensity of steel plate.Yet, if its add-on increase is too big, so hot rolling or cold rolling during because of embrittlement produces the crack, and therefore be limited to 0.1% on it.
Al is as reductor, and in order to show this effect, requires that Al content is not less than 0.005% in the steel.On the other hand, its add-on surpasses 0.1% makes oxide compound-system inclusion increase, and causes the problem that surface quality reduces, so is limited to 0.10% on it.
Cr and Mo have during the compression moulding after heat by changing the effect that the state of alloying aluminium coat during the heat changes the state of surface crack, and because they cause the after-painting corrosion resistance of moulding product to improve therefore is important.For these elements, by the exposed erosion resistance and the after-painting corrosion resistance of sample after the high-temperature molding in result shown in the Fig. 2 and 3 that obtains by the add-on of measuring Cr and Mo and the laboratory test, the inventor finds to have to add Cr and Mo.Here, method for measuring under the condition shown in adopting in an embodiment uses the sample of taking from behind the high-temperature molding through the part of processing to estimate its exposed erosion resistance and after-painting corrosion resistance.
For among Cr and the Mo each, add excessive Cr and cause performance issue and cost to increase, and excessive Mo makes that these effects are saturated and cost is increased.Therefore the upper limit of each element fixes on 2.0% and 1.0% respectively.
To the not special regulation of other component.Comprise Ni inevitably, and if its amount in normal ranges, can not have problems.
The not special regulation of the preparation condition of steel plate of the present invention, but preferred preparation condition will be explained below.
The steel casting that will have above-mentioned component, and with the gained flat plate heat directly or after heating, perhaps will cool off the also flat board of reheat, hot rolling.Here, almost can not discern after direct rolling flat plate heat and the reheat rolling between the difference of performance of steel.And the reheat temperature is not specific, but considers productivity preferably it to be adjusted in 1, and 000-1 is in 300 ℃ the scope.
As for hot rolling, can adopt conventional hot rolling method or flat board is connected with each other and rolling continuously hot rolling method when finish rolling.Consider the tolerance range of productivity and steel plate thickness, the polish temperature when preferably controlling hot rolling is not less than the Ar3 invert point.
Adopt ordinary method to carry out hot rolling cooling afterwards.In this case, consider, preferably this cooling temperature is controlled at and is not less than 550 ℃ from the angle of productivity.On the other hand, if cooling temperature is too high, the acid pickling ability is impaired, therefore preferably this cooling temperature is controlled at not to be higher than 750 ℃.
With regard to acid pickling processing or cold-rolling treatment, can use ordinary method, and with regard to ensuing aluminize processing or ensuing aluminizing-zinc processing, also can use ordinary method.That is, under the situation about handling of aluminizing, Si concentration is that 5-12% is suitable in the plating bath, and aluminizing-during zinc handled, Zn concentration was that 40-50% is suitable in the plating bath.
Here,, can use continuous electroplating equipment with non-oxidising furnace or the continuous electroplating equipment that does not have non-oxidising furnace to electroplate, as long as keep normal condition to the atmosphere in the electroplating processes.Therefore, when producing product of the present invention, do not need special control, and therefore productivity is not interfered.
Under the superincumbent working condition, before plating, surface of steel plate is not carried out metal and electroplate in advance,, also can not produce specific problem even still use when Ni electroplates in advance, Fe electroplates in advance or other metal is pre-electroplates with raising plating performance.
And, even be included in aluminium coat or Mg when being included in aluminium-zinc electrolytic coating as Mg and Zn, can not produce specific problem and can make steel plate with similar performance.
Embodiment 4
By the heating aluminium coat and be converted into alloy layer thus, i.e. Fe-Al-system coating, and be not more than 35% by the Al amount is controlled at, and thus Fe-Al-system coating is transformed into Fe+Fe
3Al (wherein being dissolved with Al and Si) contains Fe+Fe with those like this
3The electrolytic coating of other phase outside the Al is compared, and obtains more excellent workability and erosion resistance in the part that stands to process.
C: steel plate of the present invention has after moulding and is not less than 1, the high strength of 000MPa, and it is by cooling and become the structure of mainly being made up of martensite to obtain its thaumatropy thus fast after the hot rolling.In order to do like this, C content must be not less than 0.05%.On the other hand, be not less than 0.7% even C content increases to, this intensity is saturated and also be tending towards producing weld crack, so is limited to 0.7% on it.
Steel component except that C is not particularly limited, but the element of recommendation such as Si, Mn, P, Al, N, Cr, Mo, Ti, Nb, B, Ni, Cu, V, Sn, Sb etc. is as addition element or unavoidable impurities element.These elements can add when needing once in a while.Example is: Mn and B are effective aspect hardenability; Cr, Ti and Mo are effective aspect the thermotolerance of aluminium coat; And Ni and Cu improve erosion resistance.The ideal range of its adding is: Mn:0.5-3%, Si: be not higher than 1%, P: be not higher than 0.1%, S: be not higher than 0.1%, Al: be not higher than 0.1%, N: be not higher than 0.01%, Cr: be not higher than 2%, Mo: be not higher than 0.5%, Ti: be not higher than 0.5%, Nb: be not higher than 0.1%, B: be not higher than 0.05%, Ni: be not higher than 1%, Cu: be not higher than 1%, V: be not higher than 0.1%, Sn: be not higher than 0.1% and Sb: be not higher than 0.1%.
As mentioned above, aluminized deposition is more little, easy more formation Fe+Fe
3The Al zone.Under this meaning, the deposition on two sides is not more than 120g/m
2It is ideal.
Aluminum plating method has no particular limits, and can use hot dip process method, electrochemical plating, vacuum deposition method, at clad with method of another metal or the like.The most widely used industrial method is the hot dip process method at present, and often Al-10%Si is used for plating bath, wherein contains Fe as unavoidable impurities.In this case, Si enters alloy layer and Si and measures and can change with phase structure after heating.Yet, Fe+Fe
3Si amount in the Al zone is not more than 15%, and therefore this value is defined as the upper limit of Si.Add element as other, recommend to have Mn, Cr, Mg, Ti, Zn, Sb, Sn, Cu, Ni, Co, In, Bi, mishmetal etc., and, can use these elements so as long as electrolytic coating mainly is made up of Al.Add Zn and Mg and can prevent effectively that red rust from producing.Yet, add these excessive elements (its vapor pressure height) and make generation contain the smog of Zn and Mg and produce flour from the teeth outwards, or the like.Therefore, the add-on of Zn be not less than 60% and the add-on of Mg to be not less than 10% be unfavorable.
Not special aluminized pre-treatment of definition of the present invention and aftertreatment.As electroplating pre-treatment, recommend pre-electroplated Ni, Cu, Cr or Fe etc., and can adopt arbitrarily in these.As the plating aftertreatment, recommendation has chromate treating, resin coating to handle or the like, be intended to mainly prevent to get rusty with smooth, and disappearance when still being heated owing to organic resin, so it is not preferred.As for chromate treating, consider preferably to contain chromic processing film, for example electrolytic chromate or the like at present to chromic control.Also can use other aftertreatment in addition of inorganic system chromate treating.Can also use aluminum oxide, silicon-dioxide, MoS in advance
2Deng processing, be intended to smooth.
Embodiment 5
In embodiment 5, with the restriction of explaining the composition of aluminium-system coating.Therefore aluminium as herein described-system coating is meant a kind of also heating and the coating of alloying not also.
Si:Si can reduce effectively and aluminizes-thickness of the alloy layer of system (a kind of layer that is made of the intermetallic compound that forms on the interface between coating and the steel plate).And, by adding Mg, be compounded to form Mg with Si
2Si has improved erosion resistance effectively.In order to enjoy these effects, it is effective that its add-on is not less than 1%.Excessive adding Si makes fusing point raise, and single-phase on coating during crystallization as Si, and it makes erosion resistance impaired.Therefore, be limited to 15% on it.
Mg: known Mg can improve erosion resistance effectively, particularly destroys under the environment at salt.Particularly by forming Mg
2Si, the efficient that is discharged in the environment increases and the erosion resistance raising.In order to guarantee erosion resistance, the add-on of Mg is not less than 0.5%.Because excessive adding makes the surface of plating bath produce vigorous oxidation and the fusing point of plating bath is raise, and therefore its add-on is fixed on and is not more than 10%.In order to suppress the oxidation on plating bath surface, adding a small amount of Ca (being not more than 0.5%) is effectively, and can add the roughly Ca of this amount.
Zn:Zn has than Al or the lower electromotive force of steel, and has the substrate steel of inhibition corrosive function.These effects begin to occur when the Zn add-on is not less than 1%, and obtain optimum performance when the Zn amount is 20-60%.Yet add-on surpasses at 60% o'clock, and erosion resistance is impaired greatly.Therefore, lower limit and its upper limit of Zn amount fix on 1% and 60% respectively.
When reality uses the steel plate that is coated with aluminium-system of the present invention to prepare a part, after compacting, cool off part fast and quench, so this structure mainly is made of martensite with mould.For the intensity that guarantees that parts are enough, measure martensitic per-cent and be not less than 60% volume.Herein, martensitic per-cent is by polishing and etched sample, afterwards with observation by light microscope and use image analysis to calculate.
Embodiment 6
The reason of the component of regulating steel plate etc. is described below in embodiment 6.
Steel plate of the present invention has a thickness from being not less than 2 μ m to 1/10th the soft ferrite layer that is not more than steel plate thickness between intermetallic compounds layer that forms by the aluminium coat alloying and the substrate steel mainly be made of martensite.Usually, the Al of about 1-10% is present in the ferrite layer.Except Al, this ferrite also can contain Si mutually.Its thickness limits is being not less than 1 μ m.Its reason is, if the thickness of this soft ferrite layer is not more than top thickness, can not fully obtain the patience of peeling off of this coating so.On the other hand, because this layer is soft, if too thick, the intensity of whole steel plate is impaired.For this reason, determine that its upper limit is not more than 1/10th of steel plate thickness.Usually, often make an Aludip, and in this case, the aluminum-system coating on the interface between steel plate and the coating (being called " alloy layer ") is tending towards growth by the hot dip process method.If this layer growth is excessive, the workability of steel plate is impaired so, and, therefore in the plating bath that adds about 10% Si, make this Aludip.In the present invention,, need in plating bath, not add Si, even but adding Si does not have special problem yet owing to be after whole coating is heated alloying, to process Aludip while hot.
In the present invention, according to Vickers' hardness, the hardness of preferred ferrite layer is not higher than 200.As mentioned above, this layer plays a part to prevent that the stell(ite) layer from peeling off during processing.For this reason, preferably this layer is soft.Yet when this layer contained solute strengthening element such as Al, Si etc., it was harder than conventional ferrite layer.
Next, other component relevant with the present invention described.At first, about the steel component, because the present invention is intended to obtain the high intensity region that conventional TRIP steel can not obtain, and by the enhancing intensity of quenching, ideal C amount is not less than 0.05%, preferably is not less than 0.1%.Other element as in the steel uses elements such as Si, Mn, Ti, B, Cr, Mo, Al, P, S, N usually.Si is effective aspect fatigue characteristic, and Mn and B help improving hardenability.Ti, Si, Cr, Mo and Al improve stable on heating element after aluminizing.
As for the structure of aluminium coat, as mentioned above, aluminium coat mainly is made up of Al and can be contained Si.As other addition element, recommend to have Cr, Mg, Ti, Sb, Sn, Zn etc., and as long as this coating mainly is made up of Al, they can use all so.Yet the boiling point of Zn is low, and when excessive use, during heating Zn produces zinc powder in its surface, so during pressing causes wearing and tearing.Therefore, to be not less than 60% be unfavorable to its add-on.
The component that produces in aluminum-system coating has FeAl
3, Fe
2Al
5, Fe
3Al, Fe
2Al
5Si etc.These are tending towards forming multilayered structure with laminated form mutually, but the structure of these phases ad hoc rules not.When its composition mainly is made of Al and Fe, and when joining Si in the aluminium plating bath, it contains the Si of the 5-10% that has an appointment.These elements account in all are formed and are not less than 90%.And, can remain with a small amount of not Al of alloying, but as long as its amount is little, it does not influence the performance of Aludip.
Thickness with the light microscope determining ferrite layer.By with cross section polishing, and use afterwards about 2% nital etching it, clearly observe the thickness of ferrite layer.Yet, there is a kind of situation that almost can not observe the border of intermetallic compounds layer, in this case, adopt EPMA to analyze in addition.Like this, can easily identify ferrite layer by the difference of the intensity of radioactivity between Fe and the Al.It is by the thickness of measuring about 5 random partials and calculates the Determination of thickness that its mean value carries out ferrite layer and determine.And substrate steel is made up of the structure of mainly being made up of martensite, and for example can be by arriving this structure with the picral etching and with observation by light microscope.
Fig. 7 has shown the example of structure of the present invention.Recognize two-layerly at the interface at it, and according to the result of EPMA quantitative analysis, lower floor is that thickness is the ferrite layer of about 5 μ m.In Fig. 7 of this paper, label 1 this layer of demonstration is made up of Al:26.85%, Si:9.83%, Fe:59.92%; Label 2 demonstrations consist of Al:49.54%, Si:3.11%, Fe:44.89%; Label 3 demonstrations consist of Al:30.75%, Si:8.88%, Fe:56.91%; Label 4 demonstrations consist of Al:9.59%, Si:2.92%, Fe:84.02%.
At last, the heating and cooling condition for the coating steel plate has no particular limits the heating and cooling method.In order to obtain hardening structure, in fact rate of cooling influences it greatly, and rate of cooling to be not less than about 30 ℃/second be ideal.This depends on the steel component, and for steel with good hardenability, the main ideal structure of forming by martensite even can under about 10 ℃/second rate of cooling, obtain, perhaps in another case, require rate of cooling to be not less than 100 ℃/second, this depends on the steel grade.In order to obtain the ferrite layer of desired thickness, need make the heating condition optimizing.
Embodiment 7
The reason of regulating steel plate composition etc. is described below in embodiment 7.
The present invention be a kind of after moulding, have be not less than about 1, the high-intensity high tensile steel plate of 000Mpa, and it is after standing hot rolling or local fast heating, the steel plate that its quenching is obtained by quick cooling, do like this, be converted into the structure of mainly forming by martensite.Therefore, the hardness of mensuration substrate steel is not less than 250.This hardness is measured according to Vickers' hardness.In order to obtain this hardness, the C amount is 0.05% to be ideal.Other element as in the steel has no particular limits, but frequent elements Si, Mn, Ti, B, Cr, Mo, Al, P, S, the N etc. of using.Si is effective aspect fatigue characteristic, and Mn and B help improving hardenability.Ti, Si, Cr, Mo and Al improve stable on heating element after aluminizing.
And by an aluminum-system coating of mainly being made up of Al and Fe, and the thickness limits of this aluminum-system coating is at 3-35 μ m on the surface of substrate steel for steel plate of the present invention, preferably 3-18 μ m.As mentioned above, this restriction is to consider that the balance between weldability, after-painting corrosion resistance and the thermotolerance is just definite.That is,, can not obtain enough after-painting corrosion resistances and thermotolerance when bed thickness during less than 3 μ m.Particularly do not add in aluminium coat under the situation of Si, thermotolerance is impaired obviously.But determine the upper limit of its thickness by spot weldability.When electroplating thickness is not more than 35 μ m, but can obtain the spot weldability identical (electrode life) with steel plate galvanized; And when electroplating thickness is not more than 18 μ m, but can obtain the spot weldability identical with the hot dipping alloy galvanized steel plate.Can be with FeAl
3, Fe
2Al
5, Fe
3Al, Fe
2Al
8Si etc. form alloy layer.And, the formation that can discern the ferrite layer that contains Al at the interface frequently between alloying layer and substrate steel.
Usually, in Aludip, Fe-Al-system alloying layer is tending towards growth and destroys workability.Therefore, Si often takes place to add to suppress the alloy layer growth and to improve workability.Under the hot rolled situation,, therefore not to need to add Si especially because steel plate is heated and alloying processing while hot to its surface at aluminium coat.Yet, in fact also can add Si.The part steel plate is being carried out under the situation of rapid heating, owing at room temperature process, so the adding of Si is essential.Recommend Cr, Mg, Ti, Sb, Sn, Zn etc. as other addition element in the aluminium coat, and as long as this coating mainly is made up of Al, these elements can use so.Yet the boiling point of Zn is low, and when excessive use, during heating Zn produces zinc powder in its surface, so during pressing causes wearing and tearing.Therefore, to be not less than 60% be unfavorable to its add-on.
Not special galvanized pre-treatment of definition of the present invention and aftertreatment, and the heating means and the method for cooling thereof of steel plate during the compacting.As electroplating aftertreatment, recommendation has chromate treating, resin coating to handle or the like, is intended to mainly prevent to get rusty with smooth, yet,, consider at present to chromic control as for chromate treating, preferably contain chromic processing film, for example electrolytic chromate or the like.Can use resin coating to handle and can improve formability effectively usually, and effective especially during with a part of steel plate rapid heating after moulding.When steel plate was heated moulding then, resin film decomposed, therefore not influence.
Preparation method to Aludip does not stipulate yet.Can use conventional system steel bar spare and hot-rolled condition.Often aluminize, but method is not limited to this, can uses plating, vapor deposition processing etc. in anhydrous solvent by the hot dip process method.Recommend to have the pre-plating of Ni etc. as the pre-treatment before electroplating, and can adopt it.
The also not special regulation of the method for heating or cooling metal sheets.Can adopt a kind of heating unit such as electrically heated, heating, ratio-frequency heating etc. in stove.In these devices, ratio-frequency heating is fit to fast the part steel plate be heated.
Embodiment 8
The reason of regulating steel plate component etc. is described below in embodiment 8.
As mentioned above, the present invention a kind ofly cools off it afterwards immediately by forming Aludip while hot after the heating, and thus it is quenched guaranteeing the technology of desirable strength, and requires the component of steel plate to give the hardenability of this steel plate excellence.In order to satisfy this requirement, require the C amount to be not less than 0.05%, preferably be not less than 0.1%.Other element as in the steel often uses elements Si, Mn, Ti, B, Cr, Mo, Al, P, S, N etc.Si is effective aspect fatigue characteristic, and Mn and B help improving hardenability.Ti, Si, Cr, Mo and Al improve stable on heating element after aluminizing.
Can produce aluminum-system coating component from the teeth outwards after the heating FeAl is arranged
3, Fe
2Al
5, Fe
3Al, Fe
2Al
5Si etc.These are tending towards forming multilayered structure with laminated form mutually, but the structure of these phases ad hoc rules not.When its composition mainly is made of Al and Fe, and when joining Si in the aluminium plating bath, wherein contain the Si of the 5-10% that has an appointment.These elements account in all are formed and are not less than 90%.And being heated at coating is transformed into aluminum-system coating to its surface, just Aludip is stood press process.This be because, when Al stayed the surface in a large number and goes up, weldability and after-painting corrosion resistance were impaired.
As for heating and cooling condition of the present invention, the heating and cooling method is had no particular limits.Can use any one type of heating, for example heating in atmospheric furnace, induction heating, electrically heated etc.The heating rate of this moment also without limits.Heating rate in fact depends on the thickness and the shape of steel plate greatly.Recently learn, in stove the residence time long more, the adherence of coating between ensuing shaping period is good more.Heating temperature is roughly at 800-1, in 200 ℃ the scope, and preferred 900-1,000 ℃, and importantly keep steel plate in this temperature range, to continue about several minutes.Yet the residence time is depended on temperature, and definite this residence time must be longer than the time of following four conditions: A (800 ℃, 13 minutes), B (900 ℃, 6 minutes), C (1,050 ℃, 1.5 minutes) and D (1,200 ℃, 0.3 minute).
Yet the productivity when the long residence time makes compression moulding is impaired.By 950 ℃ down heating can obtain in fact enough adherence of coatings in 5-8 minute, this condition is as trade-off points and definite.Hardening structure is subjected to the influence of rate of cooling in fact greatly, and in order to obtain described hardening structure, requires rate of cooling to be not less than 10 ℃/second.This depends on the steel component, and under for the situation of steel plate with good hardenability, even under about 10 ℃/second rate of cooling, also can obtain the main desired structure of forming by martensite, perhaps in another case, it is about 30 ℃/second according to steel class requirement rate of cooling.
Next, be that the present invention is explained on the basis in detail with embodiment.
Embodiment 1
To applying hot dip aluminum plating as the acid pickling steel plate (thick 1.8mm) of material and cold-rolled steel sheet (thick 1.2mm) (have the steel shown in the table 1 form and make) by conventional hot rolling and cold-rolling practice.The the 1st, 3,5,7 and No. 9 in the table 1 is cold-rolled steel sheet, other be hot-rolled steel sheet.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, after immersion plating, adopt gas to wipe method (gas wiping method) galvanized deposition is adjusted to every 40g/m
2, and after this, steel plate is cooled off and stands zero zinc flower (zero-spangle) processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.The coating outward appearance is good, does not electroplate defective etc.Estimate the hardenability and the thermotolerance of the aludip that makes thus.Evaluation method is shown in down.
As the method for the alloying of reality, 950 ℃ of heating 30 minutes down, cooling afterwards is inserted between the mould that is formed from steel under nitrogen environment simultaneously with Aludip.Rate of cooling is 100 ℃/second.Naked eyes are estimated peeling off of steel plate coating.In addition, apply the Vickers' hardness of measuring the steel plate cross section under the 100g load.Afterwards, steel plate is stood to be usually used in aluminized chemical treatment, and zinc-plated, and coating thickness is cationic electrodeposition lacquer (Nippon Paint Co., the Ltd. of 20 μ m; Powernix 110), cure, and after cutting out cross shape, stand 20 days salt spray test (JIS-Z2371), and measure the depth of corrosion of cruciform cutting part.Here, the degree of depth of cruciform cutting is about 50 μ m.Therefore, deducting the value that 50 μ m obtain by record value is real depth of corrosion.And, in order to obtain Mn in the Fe-Al intermetallic compound and the concentration of Cr, after the quenching, from the surface to 5 parts of the cross section in the dark zone of 5 μ m through polishing, use EPMA to measure the amount of Mn and Cr by quantitative analysis one sample.Evaluation result is shown in table 2.
Stable on heating judgement criteria
Zero: do not peel off
△: peel off from the edge section
*: produce and peel off
The judgement criteria of after-painting corrosion resistance
Zero: depth of corrosion is not more than 80 μ m
*: depth of corrosion is greater than 80 μ m
(each value comprises the degree of depth of cruciform cutting.)
Table 1
| Numbering | Chemical constitution (quality %) | |||||||||||
| ??C | ??Si | ??Mn | ??P | ??S | ??Al | ??N | ??Ti | ??Cr | ??Mo | ??B | ??Ti * | |
| ??1 | ??0.23 | ??0.12 | ??1.21 | ??0.02 | ??0.009 | ??0.03 | ??0.004 | ??0.02 | ??0.13 | ??- | ??0.002 | ??0.76 |
| ??2 | ??0.21 | ??0.20 | ??0.81 | ??0.02 | ??0.007 | ??0.05 | ??0.004 | ??0.22 | ??0.20 | ??- | ??- | ??0.83 |
| ??3 | ??0.17 | ??0.15 | ??1.24 | ??0.01 | ??0.008 | ??0.03 | ??0.003 | ??0.01 | ??1.10 | ??- | ??0.0008 | ??1.73 |
| ??4 | ??0.42 | ??0.7 | ??2.41 | ??0.01 | ??0.009 | ??0.01 | ??0.003 | ??0.66 | ??0.21 | ??- | ??0.001 | ??2.08 |
| ??5 | ??0.23 | ??0.31 | ??1.54 | ??0.02 | ??0.007 | ??0.05 | ??0.003 | ??0.02 | ??0.44 | ??- | ??0.002 | ??1.23 |
| ??6 | ??0.25 | ??0.18 | ??1.22 | ??0.01 | ??0.01 | ??0.04 | ??0.003 | ??0.02 | ??0.66 | ??0.20 | ??0.005 | ??1.29 |
| ??7 | ??0.24 | ??0.2 | ??0.41 | ??0.01 | ??0.02 | ??0.05 | ??0.004 | ??0.09 | ??0.10 | ??0.15 | ??0.01 | ??0.47 |
| ??8 | ??0.2 | ??0.2 | ??2.43 | ??0.01 | ??0.01 | ??0.04 | ??0.003 | ??0.09 | ??0.21 | ??- | ??0.0008 | ??1.52 |
| ??9 | ??0.03 | ??0.1 | ??1.4 | ??0.02 | ??0.01 | ??0.03 | ??0.004 | ??0.25 | ??0.15 | ??- | ??0.0003 | ??1.1 |
| ??10 | ??0.23 | ??0.12 | ??0.3 | ??0.01 | ??0.008 | ??0.05 | ??0.003 | ??0.03 | ??0.23 | ??- | ??- | ??0.41 |
| ??11 | ??0.24 | ??0.10 | ??0.51 | ??0.01 | ??0.008 | ??0.03 | ??0.004 | ??0.05 | ??0.03 | ??- | ??0.0022 | ??0.34 |
Annotate 1) Ti
*: Ti+0.5Mn+Cr+0.5Mo
Table 2
| Numbering | The Mn+Cr amount | Thermotolerance | Vickers' hardness | After-painting corrosion resistance |
| ????1 | ???0.4 | ????○ | ????515 | ??○ |
| ????2 | ???0.22 | ????○ | ????480 | ??○ |
| ????3 | ???0.96 | ????○ | ????405 | ??○ |
| ????4 | ???0.85 | ????○ | ????766 | ??○ |
| ????5 | ???0.30 | ????○ | ????511 | ??○ |
| ????6 | ???0.30 | ????○ | ????548 | ??○ |
| ????7 | ???0.15 | ????○ | ????539 | ??○ |
| ????8 | ???0.78 | ????○ | ????466 | ??○ |
| ????9 | ???0.44 | ????○ | ????200 | ??○ |
| ????10 | ???0.19 | ????○ | ????311 | ??○ |
| ????11 | ???0.21 | ????△ | ????522 | ??○ |
When C measured when low, as the 9th steel plate, its intensity reduces.In general, by Vickers' hardness being multiply by 3 values (MPa) that obtain near the strength of materials, and in this case, obtain at most only other intensity of 600Mpa level.When to the add-on of quenching effective elements (for example Mn, B etc.) hour, as No. 10 steel plate, even the C amount can not obtain quenching effect greatly, and this intensity is tending towards impaired to a certain extent.And, at Ti
*: under the little situation of the value of Ti+0.5 * Mn+Cr+0.5 * Mo, as the o.11 steel plate, coating is peeled off and thermotolerance is tending towards impaired to a certain extent after the heating.In the 1-8 steel plate, wherein the add-on of these elements in steel suitably controlled, and intensity, thermotolerance and after-painting corrosion resistance all demonstrate good result.
Next, the present embodiment No. 7 steel plate electroplated mainly containing Al-10%Si-2%Fe and wherein add in the plating bath of Mn and Cr in the table 1.Galvanized deposition is each face 60g/m
2, and obtain good plating outward appearance.After heating, steel plate was quenched 2 minutes down at 900 ℃ with mould.Rate of cooling is about 100 ℃/second.Mn in plating bath this moment and amount and the evaluation result of Cr are shown in table 3.Mn in intermetallic compound and the amount of Cr hour, as No. 1 steel plate, after-painting corrosion resistance is poor, but along with the add-on of Mn in the plating bath and Cr increases, its erosion resistance improves.Interior Mn of intermetallic compound this moment and the amount of Cr and the relation of after-painting corrosion resistance are shown in Fig. 3.Be understood that after-painting corrosion resistance improves with the amount increase of Mn and Cr.
Table 3
| Numbering | The amount of element (%) in the plating bath | The amount of intermetallic compound interior element (%) | After-painting corrosion resistance | ||
| ????Mn | ????Cr | ????Mn | ????Cr | ||
| ????1 | ????0 | ????0 | ????0.08 | ????0 | ??× |
| ????2 | ????0.1 | ????0 | ????0.11 | ????0 | ??○ |
| ????3 | ????0.2 | ????0 | ????0.24 | ????0 | ??○ |
| ????4 | ????0.4 | ????0.05 | ????0.51 | ????0.08 | ??○ |
| ????5 | ????0.6 | ????0 | ????0.73 | ????0 | ??○ |
| ????6 | ????0.8 | ????0.1 | ????0.75 | ????0.14 | ??○ |
Embodiment 2
The steel casting that different chemical is formed will be had shown in the table 4, be heated to 1 once more, 050-1,250 ℃ temperature, hot rolling afterwards, acid pickling, cold rolling, anneal, stand electroplating processes and (aluminize or aluminize-zinc: plating " Galvalium "), stand tempering with 0.8% shrinking percentage (reductionrate) afterwards and roll.And, as whole alloying process, these steel plates being heated to 900-1,000 ℃ temperature kept 5 minutes under this temperature, and the mould with room temperature is pressed afterwards, investigates its performance then.To the mensuration of material performance is partly to cut sample by quick refrigerative when rolling, and it is applied tension test carries out.This test is according to JIS-Z2201 sample to be cut into 5 test films, and carry out according to the measuring method described in the JIS-Z2241.Evaluation result is shown in table 5.
Table 4
| Grade of steel | ??C | ??Si | ??Mn | ??S | ??P | ??Al | ??Ti | ??N | ??Ni | ??Cu | ??B | ??Sn | ????Ti-3.42 *N |
| ?1 | ??0.22 | ??0.20 | ??1.05 | ??0.020 | ??0.020 | ??0.025 | ??0.020 | ??0.0024 | ??0.02 | ??0.02 | ??0.0030 | ??- | ????0.012 |
| ?2 | ??0.21 | ??0.15 | ??0.94 | ??0.018 | ??0.023 | ??0.024 | ??0.022 | ??0.0035 | ??0.25 | ??0.10 | ??0.0027 | ??- | ????0.010 |
| ?3 | ??0.22 | ??0.15 | ??0.94 | ??0.018 | ??0.023 | ??0.024 | ??0.022 | ??0.0025 | ??0.01 | ??0.01 | ??0.0027 | ??0.01 | ????0.013 |
| ?4 | ??0.16 | ??0.48 | ??1.70 | ??0.009 | ??0.015 | ??0.021 | ??0.017 | ??0.0025 | ??0.80 | ??0.02 | ??0.0002 | ??- | ????0.008 |
| ?5 | ??0.35 | ??0.05 | ??1.00 | ??0.015 | ??0.012 | ??0.030 | ??0.020 | ??0.0028 | ??0.01 | ??0.01 | ??0.0020 | ??- | ????0.010 |
| ?6 | ??0.53 | ??0.10 | ??1.10 | ??0.010 | ??0.020 | ??0.026 | ??0.200 | ??0.0021 | ??0.02 | ??0.01 | ??0.0010 | ??0.05 | ????0.193 |
| ?7 | ??0.53 | ??0.10 | ??0.30 | ??0.010 | ??0.020 | ??0.030 | ??0.020 | ??0.0020 | ??0.90 | ??0.02 | ??0.0047 | ??- | ????0.013 |
| ?8 | ??0.22 | ??0.20 | ??1.00 | ??0.002 | ??0.015 | ??0.035 | ??0.005 | ??0.0034 | ??0.02 | ??0.02 | ??0.0005 | ??- | ????-0.007 |
| ?9 | ??0.21 | ??0.20 | ??1.10 | ??0.022 | ??0.021 | ??0.028 | ??0.020 | ??0.0026 | ??0.00 | ??0.02 | ??0.0020 | ??- | ????0.011 |
| ?10 | ??0.22 | ??0.20 | ??2.00 | ??0.010 | ??0.010 | ??0.030 | ??0.020 | ??0.0033 | ??0.01 | ??0.01 | ??- | ??- | ????0.009 |
| ?11 | ??0.35 | ??0.15 | ??2.10 | ??0.012 | ??0.013 | ??0.023 | ??0.018 | ??0.0028 | ??0.05 | ??0.01 | ??- | ??0.01 | ????0.008 |
| ?12 | ??0.24 | ??0.20 | ??2.50 | ??0.008 | ??0.009 | ??0.035 | ??0.026 | ??0.0035 | ??0.02 | ??0.01 | ??- | ??- | ????0.014 |
Table 5
| Grade of steel | Cooling temperature (℃) | Annealing temperature (℃) | Electroplate type | TS (Mpa) before the moulding | Heating temperature before the moulding (℃) | ??YP ??(MPa) | ??TS ??(MPa) | Exposed erosion resistance | After-painting corrosion resistance |
| ??1 | ??630 | ??780 | Aluminize | ??560 | ??950 | ??1250 | ??1580 | ??○ | ??○ |
| ??610 | ??775 | Plating Galvalium | ??550 | ??950 | ??1255 | ??1600 | ??○ | ??○ | |
| ??2 | ??680 | ??760 | Aluminize | ??550 | ??950 | ??1220 | ??1610 | ??○ | ??○ |
| ??650 | ??780 | Plating Galvalium | ??558 | ??950 | ??1210 | ??1590 | ??○ | ??○ | |
| ??3 | ??620 | ??730 | Aluminize | ??570 | ??950 | ??1280 | ??1550 | ??○ | ??○ |
| ??630 | ??730 | Plating Galvalium | ??564 | ??950 | ??1270 | ??1540 | ??○ | ??○ | |
| ??4 | ??650 | ??830 | Aluminize | ??500 | ??980 | ??1110 | ??1310 | ??○ | ??○ |
| ??660 | ??840 | Plating Galvalium | ??508 | ??980 | ??1100 | ??1320 | ??○ | ??○ | |
| ??5 | ??630 | ??770 | Aluminize | ??603 | ??950 | ??1480 | ??1830 | ??○ | ??○ |
| ??640 | ??770 | Plating Galvalium | ??605 | ??950 | ??1490 | ??1820 | ??○ | ??○ | |
| ??6 | ??650 | ??775 | Aluminize | ??654 | ??940 | ??1610 | ??1990 | ??○ | ??○ |
| ??660 | ??780 | Plating Galvalium | ??660 | ??940 | ??1620 | ??1980 | ??○ | ??○ | |
| ??7 | ??650 | ??760 | Aluminize | ??780 | ??910 | ??1850 | ??2100 | ??○ | ??○ |
| ??650 | ??760 | Plating Galvalium | ??774 | ??910 | ??1820 | ??2120 | ??○ | ??○ | |
| ??8 | ??650 | ??790 | Aluminize | ??553 | ??950 | ??750 | ??980 | ??○ | ??○ |
| ??9 | ??630 | ??800 | Aluminize | ??558 | ??950 | ??1210 | ??1540 | ??× | ??○ |
| ??10 | ??640 | ??780 | Aluminize | ??554 | ??950 | ??1240 | ??1580 | ??○ | ??○ |
| ??630 | ??775 | Plating Galvalium | ??550 | ??950 | ??1230 | ??1575 | ??○ | ??○ | |
| ??11 | ??650 | ??760 | Aluminize | ??572 | ??950 | ??1200 | ??1510 | ??○ | ??○ |
| ??650 | ??760 | Plating Galvalium | ??563 | ??950 | ??1205 | ??1520 | ??○ | ??○ | |
| ??12 | ??620 | ??730 | Aluminize | ??595 | ??950 | ??1270 | ??1560 | ??○ | ??○ |
| ??630 | ??730 | Plating Galvalium | ??598 | ??950 | ??1275 | ??1570 | ??○ | ??○ |
During compression moulding, cut sample, and estimate exposed erosion resistance and after-painting corrosion resistance as the surface property after the high-temperature molding through the part of processing.Continue to estimate over 3 days exposed erosion resistance by making sample stand wet jar of test (relative humidity: 95%, temperature: 40 ℃); On sample, cut out the cruciform cut channel, estimate after-painting corrosion resistance by the salt spray test (JIS-Z2134) that makes sample stand to continue 30 days then.Adopt the cationic electrodeposition lacquer as spraying paint in this case, and the thickness that sprays paint is 15 μ m.Judge its exposed erosion resistance from its outward appearance, and applying marking zero or * come mark, its judgement criteria is: red rust takes place in * representative, zero representative does not have red rust.Equally, judge after-painting corrosion resistance from its outward appearance, and applying marking zero, △ or * come mark, its judgement criteria is: on behalf of blistering, zero be not more than 2mm, △ represents blistering greater than 2mm but be not more than 4mm, and * represent blistering greater than 4mm.The 1-7 steel is the steel of component in scope of the present invention, and all steel plates of producing under the condition in scope of the present invention can guarantee high strength after high-temperature molding, and, all no problem aspect exposed erosion resistance and after-painting corrosion resistance.Here, under the situation of No. 7 steel, also shown the result of the steel plate that under these conditions (annealing temperature derives from scope of the present invention), makes, and, in this case,, therefore do not estimate these performances because armor plate strength is too high.Under the situation of the 8th and No. 9 steel, steel plate is formed and is departed from the scope of the present invention.As a result, under the situation of No. 8 steel, the intensity (being a target of the present invention) after the high-temperature molding is low, and under the situation that is No. 9 steel, can't guarantee exposed erosion resistance and after-painting corrosion resistance.
Embodiment 3
With having the steel casting that different chemical is formed shown in the table 6, be heated to 1 once more, 050-1,250 ℃ temperature, hot rolling afterwards, acid pickling, cold rolling, anneal, stand electroplating processes (aluminize or aluminize-zinc), stand tempering with 0.8% shrinking percentage afterwards and roll.And, as whole alloying process, these steel plates being heated to 900-1,000 ℃ temperature kept 5 minutes under this temperature, and the mould with room temperature is pressed afterwards, investigates its performance then.To the mensuration of material performance is partly to cut sample by quick refrigerative when rolling, and it is applied tension test carries out.This test is sample is cut into 5 test films and to carry out according to the measuring method described in the JIS-Z2241 according to JIS-Z2201.Evaluation result is shown in table 7.
Table 6
| Grade of steel | ??C | ????Si | ????Mn | ????S | ??P | ??Al | ??N | ??Cr | ??Mo | ????Cr+7×Mo | Annotate |
| ????1 | ??0.16 | ????0.20 | ????0.72 | ????0.006 | ??0.020 | ??0.035 | ??0.0025 | ??1.00 | ??0.18 | ????2.260 | The embodiment of the invention |
| ????2 | ??0.21 | ????0.21 | ????0.68 | ????0.008 | ??0.018 | ??0.032 | ??0.0030 | ??0.95 | ??0.15 | ????2.000 | The embodiment of the invention |
| ????3 | ??0.50 | ????0.25 | ????0.75 | ????0.006 | ??0.020 | ??0.026 | ??0.0028 | ??0.98 | ??0.17 | ????2.170 | The embodiment of the invention |
| ????4 | ??0.23 | ????0.20 | ????1.50 | ????0.010 | ??0.015 | ??0.030 | ??0.0030 | ??0.32 | ??0.00 | ????0.320 | The embodiment of the invention |
| ????5 | ??0.22 | ????0.45 | ????2.20 | ????0.009 | ??0.010 | ??0.038 | ??0.0035 | ??0.00 | ??0.05 | ????0.350 | The embodiment of the invention |
| ????6 | ??0.23 | ????0.15 | ????0.30 | ????0.008 | ??0.012 | ??0.032 | ??0.0026 | ??1.90 | ??0.00 | ????1.900 | The embodiment of the invention |
| ????7 | ??0.21 | ????0.20 | ????0.50 | ????0.008 | ??0.010 | ??0.033 | ??0.0028 | ??0.00 | ??0.80 | ????5.600 | The embodiment of the invention |
| ????8 | ??0.22 | ????0.21 | ????0.65 | ????0.006 | ??0.015 | ??0.032 | ??0.0030 | ??0.10 | ??0.02 | ????0.240 | The embodiment of the invention |
| ????9 | ??0.22 | ????0.20 | ????0.70 | ????0.008 | ??0.014 | ??0.025 | ??0.0025 | ??0.25 | ??0.00 | ????0.250 | The embodiment of the invention |
| ????10 | ??0.21 | ????0.18 | ????0.45 | ????0.010 | ??0.012 | ??0.028 | ??0.0025 | ??0.00 | ??0.03 | ????0.210 | The comparative example |
Table 7
| Steel numbering system | Cooling temperature (℃) | Annealing temperature (℃) | Electroplate type | TS (MPa) before the moulding | Heating temperature before the moulding (℃) | ??YP ??(MPa) | ??TS ??(Mpa) | Exposed erosion resistance | After-painting corrosion resistance | Annotate |
| ??1 | ??630 | ??780 | Aluminize | ??565 | ??980 | ??1080 | ??1280 | ??○ | ??○ | The embodiment of the invention |
| ??620 | ??780 | Aluminize-zinc | ??560 | ??980 | ??1090 | ??1270 | ??○ | ??○ | The embodiment of the invention | |
| ??2 | ??650 | ??770 | Aluminize | ??605 | ??950 | ??1290 | ??1560 | ??○ | ??○ | The embodiment of the invention |
| ??650 | ??765 | Aluminize-zinc | ??600 | ??950 | ??1285 | ??1580 | ??○ | ??○ | The embodiment of the invention | |
| ??3 | ??635 | ??740 | Aluminize | ??725 | ??930 | ??1705 | ??1890 | ??○ | ??○ | The embodiment of the invention |
| ??630 | ??750 | Aluminize-zinc | ??750 | ??930 | ??1700 | ??1900 | ??○ | ??○ | The embodiment of the invention | |
| ??4 | ??645 | ??775 | Aluminize | ??500 | ??950 | ??1390 | ??1610 | ??○ | ??○ | The embodiment of the invention |
| ??650 | ??780 | Aluminize-zinc | ??508 | ??950 | ??1400 | ??1600 | ??○ | ??○ | The embodiment of the invention | |
| ??5 | ??630 | ??770 | Aluminize | ??603 | ??950 | ??1300 | ??1550 | ??○ | ??○ | The embodiment of the invention |
| ??630 | ??770 | Aluminize-zinc | ??605 | ??950 | ??1320 | ??1555 | ??○ | ??○ | The embodiment of the invention | |
| ??6 | ??650 | ??770 | Aluminize | ??654 | ??950 | ??1390 | ??1620 | ??○ | ??○ | The embodiment of the invention |
| ??640 | ??760 | Aluminize-zinc | ??660 | ??950 | ??1380 | ??1620 | ??○ | ??○ | The embodiment of the invention | |
| ??7 | ??640 | ??770 | Aluminize | ??780 | ??950 | ??1320 | ??1510 | ??○ | ??○ | The embodiment of the invention |
| ??650 | ??760 | Aluminize-zinc | ??774 | ??950 | ??1325 | ??1520 | ??○ | ??○ | The embodiment of the invention | |
| ??8 | ??630 | ??765 | Aluminize | ??553 | ??950 | ??1320 | ??1580 | ??○ | ??○ | The embodiment of the invention |
| ??635 | ??760 | Aluminize-zinc | ??555 | ??950 | ??1310 | ??1570 | ??○ | ??○ | The embodiment of the invention | |
| ??9 | ??640 | ??770 | Aluminize | ??558 | ??950 | ??1340 | ??1575 | ??○ | ??○ | The embodiment of the invention |
| ??645 | ??770 | Aluminize-zinc | ??562 | ??950 | ??1350 | ??1585 | ??○ | ??○ | The embodiment of the invention | |
| ??10 | ??630 | ??765 | Aluminize | ??554 | ??950 | ??1350 | ??1595 | ??× | ??× | The comparative example |
| ??640 | ??760 | Aluminize-zinc | ??550 | ??950 | ??1330 | ??1530 | ??× | ??× | The comparative example |
The part that stands to process during the compression moulding cuts sample, and estimates exposed erosion resistance and after-painting corrosion resistance as surface property after high-temperature molding.Exposed erosion resistance is estimated in wet jar of test by sample being stood continue 3 days (relative humidity: 95%, temperature: 40 ℃); On sample, cut out the cruciform cut channel, estimate after-painting corrosion resistance by the salt spray test (JIS-Z2134) that makes sample stand to continue 30 days then.Adopt the cationic electrodeposition lacquer as spraying paint in this case, and the thickness that sprays paint is 15 μ m.Judge its exposed erosion resistance from its outward appearance, applying marking zero or * mark, its judgement criteria is: red rust takes place in * representative, zero representative does not have red rust.Equally, judge after-painting corrosion resistance from its outward appearance, applying marking zero, △ or * mark, its judgement criteria is: on behalf of blistering, zero be not more than 2mm, △ represents blistering greater than 2mm but be not more than 4mm, and * represent blistering greater than 4mm.The 1-9 steel is the steel of component in scope of the present invention, and all steel plates of producing under the condition in scope of the present invention can guarantee high strength after high-temperature molding, and, all no problem aspect exposed erosion resistance and after-painting corrosion resistance.Under the situation of No. 10 steel, steel plate is formed and is departed from scope of the present invention, and therefore can't guarantee exposed erosion resistance and after-painting corrosion resistance.
Embodiment 4
To applying hot dip aluminum plating as the acid pickling steel plate (thick 1.8mm) of material and cold-rolled steel sheet (thick 1.2mm) (have the steel shown in the table 8 form and make) by conventional hot rolling and cold-rolling practice.The the 1st, 3,5 and No. 7 in the table 8 is cold-rolled steel sheet, other be hot-rolled steel sheet.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, wiping method by gas after electroplating, galvanized deposition is adjusted to two faces all is 80g/m
2, and after this, steel plate is cooled off and stands zero zinc flower processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.The plating outward appearance is good, does not electroplate defective etc.Performance is shown in table 9.
Estimate the hardenability and the workability of the aludip that makes thus.Workability is by following evaluation: as the method for actual alloying, Aludip was heated 10 minutes under 950 ℃ in atmosphere, cooling afterwards, be inserted into simultaneously (rate of cooling: about 30 ℃/second) between the mould that is formed from steel, it is cooled to room temperature, makes its test that experiences a shock afterwards.And, apply the Vickers' hardness of measuring the steel plate cross section under the 100g load.
The judgement criteria of workability
Zero: do not peel off
△: produce the crack
*: produce powdery and peel off
Table 8
| Numbering | Chemical constitution (weight %) | ||||||||||
| ??C | ??Si | ??Mn | ??P | ??S | ??Al | ??N | ??Ti | ??Cr | ??Mo | ??B | |
| ??1 | ??0.23 | ??0.12 | ??1.21 | ??0.02 | ??0.009 | ??0.03 | ??0.004 | ??0.02 | ??0.13 | ??- | ??0.002 |
| ??2 | ??0.21 | ??0.20 | ??0.81 | ??0.02 | ??0.007 | ??0.05 | ??0.004 | ??0.22 | ??0.20 | ??- | ??- |
| ??3 | ??0.17 | ??0.15 | ??1.24 | ??0.01 | ??0.008 | ??0.03 | ??0.003 | ??0.01 | ??1.10 | ??- | ??0.0008 |
| ??4 | ??0.23 | ??0.31 | ??1.54 | ??0.02 | ??0.007 | ??0.05 | ??0.003 | ??0.02 | ??0.44 | ??- | ??0.002 |
| ??5 | ??0.25 | ??0.18 | ??1.22 | ??0.01 | ??0.01 | ??0.04 | ??0.003 | ??0.02 | ??0.66 | ??0.20 | ??0.005 |
| ??6 | ??0.24 | ??0.2 | ??0.95 | ??0.01 | ??0.02 | ??0.05 | ??0.004 | ??0.09 | ??0.5 | ??0.15 | ??0.01 |
| ??7 | ??0.2 | ??0.2 | ??2.43 | ??0.01 | ??0.01 | ??0.04 | ??0.003 | ??0.09 | ??0.21 | ??- | ??0.0008 |
| ??8 | ??0.04 | ??0.1 | ??1.4 | ??0.02 | ??0.01 | ??0.03 | ??0.004 | ??0.25 | ??0.15 | ??- | ??0.0003 |
Table 9
| Numbering | Workability | Al amount (%) in the Fe-Al coating | Vickers' hardness |
| ????1 | ????○ | ????15 | ????515 |
| ????2 | ????○ | ????15 | ????480 |
| ????3 | ????○ | ????15 | ????405 |
| ????4 | ????○ | ????15 | ????511 |
| ????5 | ????○ | ????15 | ????548 |
| ????6 | ????○ | ????15 | ????539 |
| ????7 | ????○ | ????15 | ????466 |
| ????8 | ????○ | ????15 | ????209 |
When C amount was low relatively, as in No. 8 steel, its intensity was also low relatively.In general, by Vickers' hardness being multiply by 3 values (MPa) that obtain near tensile strength of material, and in this case, obtain at most only other intensity of 600Mpa level.Under the situation that is the 1-7 steel, intensity and workability all show good result.Use the EPMA quantitative analysis amount of Al in the Fe-Al coating in this case, and this value is about 15%.Here, this value is by also this analytical data on average being obtained from the surface to 5 parts of the dark scope inner analysis quenching back example cross section of 10 μ m.
Next, the present embodiment No. 1 steel plate Metal plating of mainly forming in the table 8 by Al-10%Si-2%Fe, and galvanized deposition is that each face is all at 60g/m
2To 200g/m
2Between.With the 950 ℃ of down heating in atmosphere of thus obtained sample, change the residence time simultaneously, estimate its workability with shock test, and the method described in by embodiment 4 the 1st is measured the amount of Al in the Fe-Al coating.As shown in table 10, its workability depends on the amount of Al in the Fe-Al coating, and when the amount of Al is not more than 35%, obtains good workability.And the amount of Al depends on the deposition and the residence time in the Fe-Al coating, and it is more little and the residence time is long more to can be understood as deposition, and diffusion is carried out abundant more, and the amount of Al is few more in the Fe-Al coating.
Table 10
| Numbering | Deposition (g/m 2) | The residence time | The amount of Al (%) in the Fe-Al coating | Workability |
| ????1 | ??60 | ????0 | ?36 | ??△ |
| ????2 | ??60 | ????1 | ?29 | ??○ |
| ????3 | ??60 | ????2 | ?17 | ??○ |
| ????4 | ??80 | ????0 | ?38 | ??× |
| ????5 | ??80 | ????1 | ?35 | ??△ |
| ????6 | ??80 | ????2 | ?20 | ??○ |
| ????7 | ??120 | ????2 | ?42 | ??× |
| ????8 | ??120 | ????4 | ?36 | ??× |
| ????9 | ??120 | ????6 | ?15 | ??○ |
| ????10 | ??200 | ????5 | ?44 | ??× |
| ????11 | ??200 | ????10 | ?38 | ??× |
| ????12 | ??200 | ????15 | ?377 | ??× |
Embodiment 5
To applying hot dip process Al-Si-Mg as the acid pickling steel plate (thick 1.8mm) of material and cold-rolled steel sheet (thick 1.2mm) (have the steel shown in the table 11 form and make) by conventional hot rolling and cold-rolling practice.A in the table 11, C, E and G number is cold-rolled steel sheet, other be hot-rolled steel sheet.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, after electroplating, wipe method galvanized deposition is adjusted to every 40g/m by gas
2, and after this, steel plate is cooled off and stands zero zinc flower processing.It is Al-8%Si-6%Mg-1%Fe-0.1%Ca that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.Electroplate outward appearance and show blinker pattern and good, do not electroplate defective etc.Preparation condition in this case is shown in table 12.
Estimate the hardenability and the erosion resistance of the hot dip process steel plate that makes thus.Evaluation method is described below.As actual alloyage process, this hot dip process steel plate is stood 5% tensile stress, heated 5 minutes down at 950 ℃ then, cooling is inserted between the steel plate simultaneously afterwards.Rate of cooling is about 30 ℃/second.Sample after the visual inspection cooling is to estimate its thermotolerance.Then, exposed erosion resistance is estimated in wet jar of test by sample being stood continue 3 days (relative humidity: 95%, temperature: 40 ℃); On sample, cut out the cruciform cut channel, estimate after-painting corrosion resistance by the salt spray test (JIS-Z2134) that makes sample stand to continue 30 days then.Adopting the cationic electrodeposition lacquer conduct thickness that sprays paint and spray paint in this case is 15 μ m.And, measure the Vickers' hardness of steel plate by applying 100 g load.
Stable on heating judgement criteria
Zero: good
△: produce the slit-like pattern from the teeth outwards
*: produce red dirt (red scales)
The judgement criteria of exposed erosion resistance
Zero: good
△: produce red rust
The judgement criteria of after-painting corrosion resistance
◎: the paint blistering is not more than 1mm
Zero: the paint blistering is not more than 2mm
△: paint blistering 2-4mm
*: the paint blistering is greater than 4mm
Table 11
| Grade of steel | ?C | ?Si | ?Mn | ?P | ?S | ?Al | ?N | ?Ti | ?Cr | ??Mo | ??Ni | ??B |
| ?A | ?0.21 | ?0.20 | ?0.81 | ?0.02 | ?0.007 | ?0.05 | ?0.004 | ?0.05 | ?0.20 | ??- | ??- | ??0.0005 |
| ?B | ?0.17 | ?0.15 | ?1.24 | ?0.01 | ?0.008 | ?0.03 | ?0.003 | ?0.15 | ?1.10 | ??- | ??- | ??0.0008 |
| ?C | ?0.42 | ?0.7 | ?2.41 | ?0.01 | ?0.009 | ?0.01 | ?0.003 | ?0.46 | ?0.21 | ??- | ??- | ??0.001 |
| ?D | ?0.23 | ?0.31 | ?1.54 | ?0.02 | ?0.007 | ?0.4 | ?0.003 | ?0.24 | ?0.44 | ??- | ??- | ??0.002 |
| ?E | ?0.25 | ?0.18 | ?1.22 | ?0.01 | ?0.01 | ?0.04 | ?0.003 | ?0.003 | ?0.66 | ??0.20 | ??- | ??0.005 |
| ?F | ?0.24 | ?0.2 | ?0.95 | ?0.01 | ?0.02 | ?0.05 | ?0.004 | ?0.001 | ?- | ??0.15 | ??0.33 | ??0.01 |
| ?G | ?0.08 | ?0.1 | ?1.4 | ?0.02 | ?0.01 | ?0.03 | ?0.004 | ?0.25 | ?0.15 | ??- | ??- | ??0.0003 |
| ?H | ?0.24 | ?0.10 | ?0.31 | ?0.01 | ?0.008 | ?0.03 | ?0.004 | ?0.21 | ?0.03 | ??- | ??- | ??0.0001 |
Table 12
| Numbering | Used steel numbering system | Exposed erosion resistance | After-painting corrosion resistance | Vickers' hardness |
| ????1 | ????A | ????○ | ????○ | ????485(○) |
| ????2 | ????B | ????○ | ????○ | ????401(○) |
| ????3 | ????C | ????○ | ????○ | ????769(○) |
| ????4 | ????D | ????○ | ????○ | ????509(○) |
| ????5 | ????E | ????○ | ????○ | ????544(○) |
| ????6 | ????F | ????○ | ????○ | ????540(○) |
| ????7 | ????G | ????○ | ????○ | ????289(×) |
| ????8 | ????H | ????○ | ????○ | ????301(×) |
When C amount too hour, as in No. 7 steel plate, can not obtain enough intensity.In general, by Vickers' hardness being multiply by 3 values (MPa) that obtain near the strength of materials, and in this case, obtain at most only other intensity of 800Mpa level.When to the amount of quenching effective elements such as Mn, B etc. hour, as No. 8 steel plate, even the C amount can not obtain quenching effect greatly.Under the situation that is the 1-6 steel plate, wherein the amount of element that adds in these steel is suitably controlled, and under the situation that is Mn-B-system or Mo-Cr-Ni-system, intensity and erosion resistance all show good result.
Then, use the steel E in the table 11, the variation of forming along with the plating bath of hot dip process pipeline study that coating is formed and the coating plate property between relation.Relation between the performance after coating composition and the plating is summarized in table 13.Here, the Vickers' hardness under each situation is in the scope of 470-510.
Under the situation that is No. 8 steel plate (belonging to the Mg-Zn-system), corrosion-resistant.On the other hand, 4-7 steel plate (belonging to the Si-Mg-system) shows excellent erosion resistance.Equally, 1-3 steel plate (belonging to the Si-Mg-Zn-system) shows excellent erosion resistance.
Table 13
| Numbering | The composition of coating (quality %) | Exposed erosion resistance | After-painting corrosion resistance | |||
| ????Si | ????Mg | ????Zn | ???Ca | |||
| ??1 | ????2 | ????3 | ????40 | ???0.1 | ????○ | ????◎ |
| ??2 | ????5 | ????7 | ????20 | ???0.1 | ????○ | ????◎ |
| ??3 | ????8 | ????6 | ????10 | ???- | ????○ | ????◎ |
| ??4 | ????12 | ????8 | ????- | ???0.1 | ????○ | ????◎ |
| ??5 | ????8 | ????6 | ????- | ???0.1 | ????○ | ????◎ |
| ??6 | ????6 | ????3 | ????- | ???- | ????○ | ????◎ |
| ??7 | ????9 | ????0.5 | ????- | ???- | ????○ | ????◎ |
| ??8 | ????- | ????1 | ????3 | ???- | ????× | ????× |
Embodiment 6
To applying hot dip aluminum plating as the cold-rolled steel sheet (thick 1.2mm) of material (have the steel shown in the table 14 form and make) by conventional hot rolling and cold-rolling practice.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, wiping method by gas after electroplating, galvanized deposition is adjusted to each face all is 60g/m
2, and after this, steel plate is cooled off and stands zero flicker processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.The plating outward appearance is good, does not electroplate defective etc.The Aludip that makes thus is heated to 950 ℃, and estimates the workability (peeling off patience) of coating during the air cooling with actual alloyage process.
At this moment, by changing the thickness that heat-up time and type of heating change ferrite layer.Process by shock test, state is peeled off in the variation naked eyes judgement of processing temperature along with cooling period, and estimates the workability of coating under the minimum temperature that plating exfoliation does not take place.Here, under the situation that is this steel, even hardenability is still good under 10 ℃/second rate of cooling, even and under air cooled situation, still obtain the structure mainly formed by martensite.Fig. 8 has shown the thickness of middle ferrite layer and can obtain relation between the minimum temperature of well processed in this case.
As shown in Figure 8, should be understood that the thickness when ferrite layer is not less than 2 μ m, when preferably being not less than 4 μ m, the patience of peeling off of coating improves.When the thickness of ferrite layer is about 0.5 μ m, even the powdery of also observing coating 800 ℃ of following processing peels off.And as actual alloyage process, the workability of coating depends on galvanized deposition.Although the thickness of ferrite layer is 2 μ m, when the deposition of each face is 30g/m
2The time, the minimum temperature that obtains well processed is about 500 ℃.And, by analyzing the structure of substrate steel this moment with observation by light microscope and ensuing image analysis, and be not less than 80% structure in all cases and form by martensite.
Table 14
| ???C | ???Si | ????Mn | ???P | ???S | ???Al | ???N | ???Ti | ??Cr | ??Mo | ???B |
| ???0.36 | ???0.21 | ????0.65 | ???0.02 | ???0.006 | ???0.027 | ???0.003 | ???0.002 | ??1.01 | ??0.16 | ???0.0001 |
Embodiment 7
To applying hot dip aluminum plating as the acid pickling steel plate (thick 1.8mm) of material and cold-rolled steel sheet (thick 1.2mm) (have the steel shown in the table 15 form and make) by conventional hot rolling and cold-rolling practice.The the 1st, 3 and No. 5 in the table 15 is cold-rolled steel sheet, other be hot-rolled steel sheet.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, wiping method by gas after electroplating, galvanized deposition is adjusted to each face all is 60g/m
2, and after this, steel plate is cooled off and stands zero flicker processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.The plating outward appearance is good, does not electroplate defective etc.As actual alloyage process, the aludip that makes thus is heated to 950 ℃, by the water-cooled mold cools down, when reaching about 600 ℃, temperature stands compression moulding.Naked eyes judge that all steel plates are not all observed electrolytic coating and peeled off at the state that peels off of the electrolytic coating of the part of process bending machining.At this moment, the thickness of ferrite layer is 10-20 μ m, and the martensite per-cent in all substrate steel is not less than 80%.Here, rate of cooling is about 150 ℃/second.
Table 15
| Numbering | ?C | ?Si | ?Mn | ?P | ?S | ?Al | ?N | ?Ti | ?Cr | ??Mo | ?B |
| ?1 | ?0.22 | ?0.20 | ?0.94 | ?0.02 | ?0.007 | ?0.025 | ?0.003 | ?0.22 | ?0.05 | ??0.002 | ?0.0017 |
| ?2 | ?0.16 | ?0.17 | ?0.69 | ?0.02 | ?0.007 | ?0.037 | ?0.004 | ?0.002 | ?0.98 | ??0.17 | ?0.0001 |
| ?3 | ?0.20 | ?0.20 | ?0.67 | ?0.02 | ?0.006 | ?0.033 | ?0.003 | ?0.002 | ?0.96 | ??0.17 | ?0.0002 |
| ?4 | ?0.22 | ?0.15 | ?0.88 | ?0.03 | ?0.007 | ?0.022 | ?0.004 | ?0.55 | ?0.12 | ??0.01 | ?0.0005 |
| ?5 | ?0.25 | ?0.55 | ?0.72 | ?0.02 | ?0.009 | ?0.025 | ?0.003 | ?0.31 | ?0.58 | ??0.12 | ?0.0020 |
Embodiment 8
To applying hot dip aluminum plating as the cold-rolled steel sheet (thick 1.2mm) of material (have the steel shown in the table 16 form and make) by conventional hot rolling and cold-rolling practice.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, wiping method by gas after electroplating, galvanized deposition is adjusted to each face all is 30-80g/m
2, and after this, steel plate is cooled off and stands zero flicker processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.The plating outward appearance is good, does not electroplate defective etc.Hardness after the quenching of the Aludip that evaluation makes thus, thickness, weldability, thermotolerance and the after-painting corrosion resistance of intermetallic compound.As actual alloyage process, by with steel plate in atmosphere 950 ℃ down heating quenched in 0.5-20 minute, afterwards under dull and stereotyped state with mould with this steel plate compacting and with its cooling.At this moment, speed of cooling is about 300 ℃/second.Do like this, by changing alloy layer and the extremely surperficial quenched nickelclad of alloying that obtains deposition and heat-up time to have different thickness.Here, the outward appearance of all steel plates is almost even.And the evaluation method and the judgement criteria of these performances show below.
Table 16
| Numbering | ?C | ??Si | ??Mn | ??P | ??S | ??Al | ??N | ??Ti | ??Cr | ??Mo | ??B |
| ??1 | ?0.22 | ??0.20 | ??0.94 | ??0.02 | ??0.007 | ??0.025 | ??0.003 | ??0.22 | ??0.05 | ??0.002 | ??0.0017 |
[hardness]
Centre portions at the cross section of steel plate is measured Vickers' hardness by giving 100g load.
[thickness of intermetallic compound]
By using the cross section of microscopic examination steel plate, use then the 2%nitral etching it, analyze the thickness that this structure is measured intermetallic compound with EPMA afterwards.An analysis example is shown in Fig. 9.Label 1 shows the layer with following composition: Al:26.85%, Si:9.83%, Fe:59.92%; Label 2 shows the layer with following composition: Al:49.54%, Si:3.11%, Fe:44.87%; Label 3 shows the layer with following composition: Al:30.75%, Si:8.88%, Fe:56.91%; Show layer with label 4: Al:9.59%, Si:2.92%, Fe:84.02% with following composition.
[weldability]
But estimate spot weldability under the following conditions:
Electrode: make and have the Dome electrode of 6 φ-40R top electrode by the aluminum oxide that is dispersed with copper,
Pressure: 600kgf,
Welding current: 10kA,
Weld interval: 12 cycles (60Hz).
Judgement criteria:
Zero: greater than the series spot welding in 2,000 cycles
△: 1,200-2, the series spot welding in 000 cycle
*: less than the series spot welding in 1,200 cycle
[after-painting corrosion resistance]
In chemical pretreatment solution (being usually used in aluminizing of steel plate), a steel plate is stood about 2 minutes chemical treatment with zinc-plated, coating thickness is the cationic electrodeposition lacquer of 20 μ m then, toasted 20 minutes down at 140 ℃, after cutting out the cruciform cut channel, stand 20 days salt spray test, and judge after-painting corrosion resistance according to the depth of corrosion of cruciform cut channel part.The degree of depth of the cruciform cut channel that cuts out with cutting machine is about 50 μ m herein.Therefore, deducting the value that 50 μ m obtain by measured value is real depth of corrosion.
Evaluation result is summarized in table 17.
Judgement criteria
Zero: depth of corrosion is not more than 80 μ m
*: depth of corrosion is greater than 80 μ m
Table 17
| Numbering | The thickness of alloy layer (μ m) | The hardness of base material (Hv) | But spot weldability | After-painting corrosion resistance |
| ??1 | ?2 | ????397 | ??○ | ????× |
| ??2 | ?5 | ????395 | ??○ | ????○ |
| ??3 | ?10 | ????399 | ??○ | ????○ |
| ??4 | ?17 | ????401 | ??○ | ????○ |
| ??5 | ?25 | ????398 | ??△ | ????○ |
| ??6 | ?32 | ????399 | ??△ | ????○ |
| ??7 | ?38 | ????397 | ??× | ????○ |
Shown in table 17, when the thickness of alloy layer hour, but steel plate is tending towards having excellent spot weldability, but after-painting corrosion resistance is relatively poor.When this thickness was too thin, as No. 1 steel plate, this steel plate had relatively poor after-painting corrosion resistance, and when this thickness was too thick, as No. 7 steel plate, but this steel plate had relatively poor spot weldability.Equally, under the situation that is the 5th and No. 6 steel plate, but steel plate is tending towards having relatively poor spot weldability.Therefore, but when thinking that spot weldability is important, it is comparatively ideal making the thickness relative thin of alloy layer.
Embodiment 9
With the Metal plating of mainly forming of the prepared steel plate of the steel that shows in the table 18, and observe good plating outward appearance by Al-10%Si-2%Fe.Be determined at the thickness that descends quenching alloy layer afterwards with the 1st the same terms of embodiment 7, these are worth in the scope of 8-15 μ m.For these steel plates, estimate the 1st identical scoring item with embodiment 7.As a result, all steel plates acquisitions are equivalent to the evaluation result of the opinion rating zero of embodiment 1, and show good weldability and good after-painting corrosion resistance.
Table 18
| Numbering | ??C | ??Si | ??Mn | ??P | ??S | ??Al | ??N | ??Ti | ??Cr | ??Mo | ??B |
| ??1 | ??0.22 | ??0.20 | ??0.94 | ??0.02 | ??0.007 | ??0.025 | ??0.003 | ??0.22 | ??0.05 | ??0.002 | ??0.0017 |
| ??2 | ??0.16 | ??0.17 | ??0.69 | ??0.02 | ??0.007 | ??0.037 | ??0.004 | ??0.002 | ??0.98 | ??0.17 | ??0.0001 |
| ??3 | ??0.20 | ??0.20 | ??0.67 | ??0.02 | ??0.006 | ??0.033 | ??0.003 | ??0.002 | ??0.96 | ??0.17 | ??0.0002 |
| ??4 | ??0.36 | ??0.21 | ??0.65 | ??0.02 | ??0.006 | ??0.027 | ??0.003 | ??0.002 | ??1.01 | ??0.16 | ??0.0001 |
| ??5 | ??0.22 | ??0.15 | ??0.88 | ??0.03 | ??0.007 | ??0.022 | ??0.004 | ??0.55 | ??0.12 | ??0.01 | ??0.0005 |
| ??6 | ??0.25 | ??0.55 | ??0.72 | ??0.02 | ??0.009 | ??0.052 | ??0.003 | ??0.31 | ??0.58 | ??0.12 | ??0.0020 |
| ??7 | ??0.23 | ??0.18 | ??0.21 | ??0.03 | ??0.007 | ??0.025 | ??0.003 | ??0.27 | ??0.03 | ??0.01 | ??0.0022 |
Embodiment 10
To applying hot dip aluminum plating as the cold-rolled steel sheet (thick 1.2mm) of material (have the steel shown in the table 19 form and make) by conventional hot rolling and cold-rolling practice.In the time of hot dip aluminum plating, use the pipeline of non-oxidising furnace hearth type reduction, wiping method by gas after electroplating, galvanized deposition is adjusted to each face all is 60g/m
2, and after this, steel plate is cooled off and stands zero flicker processing.It is Al-10%Si-2%Fe that the plating bath of this moment is formed.Fe in the plating bath is the component that the steel plate in electroplating device and the plating bath provides inevitably.The plating outward appearance is good, does not electroplate defective etc.The aludip that makes is thus heated in atmosphere, remain under the differing temps then, and form shape shown in Figure 10.At this moment, with the water-cooled mould these steel plates are cooled off.Heating rate is about 5-10 ℃/second, and the rate of cooling each several part is not quite similar, and it is about 100 ℃/second in the high part of rate of cooling, and it is about 20 ℃/second in the low part of rate of cooling.Estimate the workability (peeling off patience) of electrolytic coating this moment.Forming electrolytic coating with strip or point-like on pressed surface peels off.Be displayed in Table 20 the relation between the state of peeling off of heating condition and electrolytic coating.In addition, heating condition of the present invention is shown in Figure 11.
Table 19
| ??C | ????Si | ????Mn | ????P | ????S | ??Al | ??N | ??Ti | ??Cr | ??Mo | ??B |
| ??0.24 | ????0.21 | ????0.95 | ????0.02 | ????0.006 | ??0.027 | ??0.003 | ??0.002 | ??1.01 | ??0.16 | ??0.0018 |
Table 20
| Numbering | Heating temperature (℃) | Heat-up time (minute) | Tack |
| ????1 | ????800 | ????20 | ????△ |
| ????2 | ????850 | ????15 | ????○ |
| ????3 | ????900 | ????13 | ????○ |
| ????4 | ????950 | ????8 | ????○ |
| ????5 | ????1000 | ????6 | ????○ |
| ????6 | ????1050 | ????4 | ????○ |
| ????7 | ????1100 | ????2 | ????○ |
| ????8 | ????900 | ????5 | ????× |
| ????9 | ????1000 | ????2 | ????× |
The judgement criteria of tack
Zero: electrolytic coating does not peel off
△: produce the crack at the parcel plating layer
*: electrolytic coating peels off
Shown in table 20, for the alloying process of reality,,, also be difficult to reach the ideal tack even heat 20 minutes if temperature is low to moderate 800 ℃.And when Heating temperature raise, the residence time was not more than 10 minutes and just obtains good tack.For the alloying process of reality, when being 5 minutes 900 ℃ of following residence time, perhaps when 1,000 ℃ of following residence time was 2 minutes, tack was still not enough.
Industrial applicibility
As mentioned above, the invention provides a kind of hot-rolling method that forms high-strength automotive part, and greatly be conducive to alleviate in future the weight of automobile.
Claims (14)
1, a kind of have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that having Fe-Al-system coating on the surface of this steel plate, contains total amount in this coating greater than 0.1% Mn and Cr.
2, a kind of have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that on the surface of this steel plate, having Fe-Al-system coating, in mass, contain total amount in this coating greater than 0.1% Mn and Cr, in mass, this steel plate contains C:0.05-0.7%, Si:0.05-1%, Mn:0.5-3%, P: be not higher than 0.1%, S: be not higher than 0.1% and Al: be not higher than 0.2%, contain one or more in addition and be selected from following element: Ti:0.01-0.8%, Cr: be not higher than 3% and Mo: be not higher than 1%, so that satisfy following formula 1:
Ti+0.5×Mn+Cr+0.5×Mo＞0.4??...1
3, as claimed in claim 2 have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that, in mass, this steel also contains one or more and is selected from following element: N: be not higher than 0.1%, Nb: be not higher than 0.1%, V: be not higher than 0.1%, Ni: be not higher than 1%, Cu: be not higher than 1%, B:0.0003-0.03%, Sn: be not higher than 0.1% and Sb: be not higher than 0.1%.
4, as claimed in claim 1 have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that, in mass, this steel contains: C:0.15-0.55%, Si: be not higher than 0.5%, Mn:0.2-3%, P: be not higher than 0.1%, S: be not higher than 0.04%, Al:0.01-0.1% and N: be not higher than 0.01%, and contain one or more and be selected from following element: B:0.0002-0.0050%, Ti:0.01-0.8%, Cr: be not higher than 2%, Mo: be not higher than 1%, Ni: be not higher than 1%, Cu: be not higher than 0.5% and Sn: be not higher than 0.2%.
5, as claim 1-4 each have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that described Fe-Al-system coating also contains the Si of 1-20%.
6, as each the alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts of claim 1-5, it is characterized in that the Al concentration in the Fe-Al-system coating is not higher than 35 weight %.
7, as claim 1-6 each have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, it is characterized in that described Fe-Al-system coating also contains one or both among Zn:1-50% and the Mg:0.1-10%.
8, as claim 1-7 each have the excellent thermotolerance and a high-intensity alloyed aluminum-system plated steel plate of after-painting corrosion resistance, the thickness that it is characterized in that described Fe-Al-system coating is 3-35 μ m.
9, a kind of alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts is characterized in that it has: the coating of mainly being made up of Fe-Al on the surface of steel plate; Thickness below this coating is from being not less than 2 μ m to 1/10th the ferrite layer that is not higher than steel plate thickness; With the substrate steel of mainly forming below this ferrite layer by martensite.
10, the alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts as claimed in claim 9 is characterized in that containing Si in aluminum-system coating on the surface of steel plate and the ferrite layer below the intermetallic compounds layer.
11,, it is characterized in that the hardness of described ferrite phase is not higher than 200 as the alloyed aluminum-system plated steel plate that is used for the high-strength vehicle parts of claim 9 or 10.
12, a kind of high-strength automotive part of compression moulding, its at least a portion are by making as each steel of claim 1-11.
13,, it is characterized in that on its surperficial at least a portion, having the plated film that thickness is 1-200 μ m as the high-strength automotive part of claim 12.
14, a kind of hot-rolling method of high-strength vehicle parts, wherein, when adopting hot-press method to prepare this trolley part, used steel plate contains the C that is not less than 0.05 weight % and makes as the steel of steel constituent with the Metal plating of mainly being made of Al, these parts be under the heating condition longer than the time of following A, B, C and D condition after the heating by compression moulding formation, and at least a portion of these parts is cooled off being not less than under 10 ℃/second the rate of cooling:
A (800 ℃, 13 minutes), B (900 ℃, 6 minutes), C (1,050 ℃, 1.5 minutes), D (1,200 ℃, 0.3 minute).
Applications Claiming Priority (22)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001181833A JP3845271B2 (en) | 2001-06-15 | 2001-06-15 | Aluminum or aluminum-galvanized steel sheet suitable for high temperature forming and having high strength after high temperature forming and method for producing the same |
| JP181833/2001 | 2001-06-15 | ||
| JP2001190708A JP4634655B2 (en) | 2001-06-25 | 2001-06-25 | Aluminized steel sheet for hot press with excellent heat resistance |
| JP190707/2001 | 2001-06-25 | ||
| JP190709/2001 | 2001-06-25 | ||
| JP2001190709A JP4564207B2 (en) | 2001-06-25 | 2001-06-25 | Hot-pressed hot-dip aluminized steel sheet that is heated to 800 ° C or higher |
| JP190708/2001 | 2001-06-25 | ||
| JP2001190707A JP4023710B2 (en) | 2001-06-25 | 2001-06-25 | Aluminum-plated steel sheet for hot press with excellent corrosion resistance and heat resistance, and automotive parts using the same |
| JP2001198431 | 2001-06-29 | ||
| JP198431/2001 | 2001-06-29 | ||
| JP220807/2001 | 2001-07-23 | ||
| JP2001220807A JP4612240B2 (en) | 2001-07-23 | 2001-07-23 | High-strength aluminized steel sheet with excellent corrosion resistance after painting and automotive parts using it |
| JP228431/2001 | 2001-07-27 | ||
| JP2001228431A JP4990449B2 (en) | 2001-07-27 | 2001-07-27 | Aluminum-coated steel sheet for high-strength automotive parts and automotive parts using the same |
| JP241633/2001 | 2001-08-09 | ||
| JP2001241633A JP4551034B2 (en) | 2001-08-09 | 2001-08-09 | High-strength aluminum plated steel sheet for automobile parts with excellent weldability and post-painting corrosion resistance, and automobile parts using the same |
| JP264727/2001 | 2001-08-31 | ||
| JP2001264727 | 2001-08-31 | ||
| JP2001383852A JP2003183802A (en) | 2001-12-18 | 2001-12-18 | High-strength aluminum-plated steel sheet excellent in heat resistance and after-coating corrosion resistance, and high-strength automotive part |
| JP383852/2001 | 2001-12-18 | ||
| JP390842/2001 | 2001-12-25 | ||
| JP2001390842A JP4022063B2 (en) | 2001-12-25 | 2001-12-25 | High-strength aluminum-plated steel sheet and high-strength automotive parts with excellent workability and corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1531604A true CN1531604A (en) | 2004-09-22 |
| CN100370054C CN100370054C (en) | 2008-02-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028120361A Ceased CN100370054C (en) | 2001-06-15 | 2002-06-14 | High-strength alloyed aluminum-system plated steel sheet and high-strength automotive part excellent in heat resistance and after-painting corrosion resistance |
Country Status (5)
| Country | Link |
|---|---|
| KR (4) | KR20070087240A (en) |
| CN (1) | CN100370054C (en) |
| AU (1) | AU2002309283B2 (en) |
| TW (1) | TWI317383B (en) |
| WO (1) | WO2002103073A2 (en) |
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2002
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100836282B1 (en) | 2008-06-09 |
| CN100370054C (en) | 2008-02-20 |
| KR20040007718A (en) | 2004-01-24 |
| WO2002103073A3 (en) | 2004-05-21 |
| AU2002309283B2 (en) | 2005-04-14 |
| KR20070119096A (en) | 2007-12-18 |
| WO2002103073A2 (en) | 2002-12-27 |
| TWI317383B (en) | 2009-11-21 |
| KR20070087240A (en) | 2007-08-27 |
| KR20080108163A (en) | 2008-12-11 |
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